Hydroxide-Catalyzed Formation Of Silicon-Oxygen Bonds By Dehydrogenative Coupling Of Hydrosilanes And Alcohols

ABSTRACT

The present disclosure is directed to methods for dehydrogenatively coupled hydrosilanes and alcohols, the methods comprising contacting an organic substrate having at least one organic alcohol moiety with a mixture of at least one hydrosilane and sodium and/or potassium hydroxide, the contacting resulting in the formation of a dehydrogenatively coupled silyl ether. The disclosure further described associated compositions and methods of using the formed products.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/384,178 filed Apr. 15, 2019 which is a divisional of U.S. patentapplication Ser. No. 15/219,710, filed Jul. 26, 2016, that claims thebenefit of priority from U.S. Patent Application Nos. 62/198,405, filedJul. 29, 2015, and 62/269,746, filed Dec. 18, 2015 the contents of whichare incorporated by reference herein for all purposes.

GOVERNMENT RIGHTS

This invention was made with government support under Grant Nos.CHE1212767 and CHE1205646 awarded by the National Science Foundation.The government has certain rights in the invention.

TECHNICAL FIELD

The present invention is directed at methods of forming silicon-oxygenbonds by dehydrogenative coupling of hydrosilanes and alcohols

BACKGROUND

The silicon-oxygen (Si—O) bond is an extremely useful feature in organicchemistry, at least for its use in protecting group chemistries, itsutility as a traceless directing group in organic synthesis, and itsprevalence in a number of important functional material classes. Thesilylative protection of alcohols has further been employed in drugdiscovery to improve pharmacokinetic properties of pharmaceuticallyrelevant molecules and to enhance drug toxicity.

A large number of catalytic methods for the construction of O—Si bondshave been developed (FIG. 1A). The direct silylation of alcohols bytransition metal catalysis or Brønsted and Lewis acids/bases andcatalytic hydrosilylation of carbonyl compounds have been the mostcommonly employed protocols. However, despite decades of work, the mostprominent method for the construction of the Si—O bond is the treatmentof alcohols with moisture-sensitive chlorosilanes in the presence ofnucleophilic catalysts and a base to scavenge the HCl generated.Moreover, in certain challenging cases such as the silylene protectionof 1,2-diols with certain silanes, the use of highly reactive or toxicelectrophilic silicon reagents is necessary. As a result, thedevelopment of an effective, general, and convenient O—Si constructionmethodology which circumvents the production of stoichiometric saltby-products and avoids the use of toxic and moisture-sensitiveelectrophilic silicon sources, while simultaneously improving the scopein comparison to previous methods would be of considerable interest tochemists working in a variety of fields.

The present invention takes advantage of the discoveries cited herein toavoid at least some of the problems associated with previously knownmethods.

SUMMARY

Herein is disclosed a mild, efficient, and generally directcross-dehydrogenative Si—O bond construction protocol employing NaOH andunactivated KOH as the catalyst is described (see, e.g., FIG. 1B). Themethod allows for the direct coupling of an O—H bond and a silane Si—Hbond to furnish the corresponding O—Si bond in a single step, withoutthe production of stoichiometric salt by-products. The catalysisproceeds under mild conditions, in the absence of transition metalsalts, hydrogen acceptors, or other additives and liberates dihydrogenas the sole by-product. The scope of the method is broad, enabling thedirect silylation of primary, secondary, and tertiary alcohols as wellas diols, polyols, and phenols in the presence of halide, nitro, andcarbonyl functionalities as well as strained rings, olefins, alkynes,and electron rich and electron deficient aromatic heterocycles. Thescope of the hydrosilane is excellent, enabling high steric andelectronic tunability of the resultant O—Si bond, which would be ofvalue in a number of applications including protecting group chemistry,materials science, and even drug discovery. Facile scalability, lowcost, and broad scope make this a practical and attractive O—Si bondconstruction strategy. Applications to directing group chemistry and amulti-gram scale synthesis of a novel cross-coupling reagent aredemonstrated.

Various embodiments includes methods comprising or consistingessentially of contacting an organic substrate having at least oneorganic alcohol moiety with a mixture of at least one hydrosilane and asodium and/or potassium hydroxide, in the absence of hydroxideactivators, the contacting resulting in the formation of adehydrogenatively coupled silyl ether. In related embodiments, themethod is conducted in the substantial absence of transition metalcatalysts, in the substantial absence of “superbases,” such asalkoxides, hydrides, alkyl lithium reagents, anionic amide or phosphinebases, or any chemical known to enhance the activity of the NaOH or KOH(e.g., crown ethers), and in the substantial absence of fluoride ion.

In the methods and the related compositions, the at least onehydrosilane comprises a hydrosilane of Formula (I) or a hydrodisilane ofFormula (II):

(R)_(3-m)Si(H)_(m+1)  (I)

(R)_(2-m)(H)_(m+1)Si—Si(R)_(3-m)(H)_(m)  (II)

where m is independently 0, 1, or 2; and each R is broadly definedherein. The hydrosilane may be monomeric, oligomeric, or polymeric, ortethered to insoluble or sparingly soluble support media.

In some embodiments, the organic substrate having at least one organicalcohol moiety has a structure of Formula (IIIA):

R¹—OH  (IIIA),

where R¹ comprises an optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₂₋₂₄ alkenyl, optionally substituted C₂₋₂₄ alkynyl,optionally substituted C₆₋₂₄ aryl, optionally substituted C₁₋₂₄heteroalkyl, optionally substituted 5- or 6-ring membered heteroaryl,optionally substituted C₇₋₂₄ aralkyl, optionally substitutedheteroaralkyl, or optionally substituted metallocene.

In other embodiments, the organic substrate having at least one organicalcohol moiety is at least a diol, having a structure of Formula (IIIB):

HO—R²—OH  (IIIB),

where R² comprises an optionally substituted C₂₋₁₂ alkylene, optionallysubstituted C₂₋₁₂ alkenylene, optionally substituted C₆₋₂₄ arylene,optionally substituted C₁₋₁₂ heteroalkylene, or an optionallysubstituted 5- or 6-ring membered heteroarylene. In some of theseembodiments, the organic substrate having at least one organic alcoholmoiety is or comprises an optionally substituted catechol moiety or hasa Formula (IV):

wherein n is from 0 to 6, preferably 0 or 1;

R^(M) and R^(N) are independently H or methyl

R^(D), R^(E), R^(F), and R^(G) are independently H, C₁₋₆ alkyl, C₁₋₆alkenyl, optionally substituted phenyl, optionally substituted benzyl,or an optionally substituted 5- or 6-ring membered heteroaryl, whereinthe optional substituents are C₁₋₃ alkyl, C₁₋₃ alkoxy, or halo. Withinthis genus, the organic substrate includes substituted 1,2-diols,1,3-diols, 1,4-diols, these being substituted with one or more alkyland/or optionally substituted aryl or heteroaryl substituents. A rangeof such diols are discussed in this disclosure. The organic substratehaving at least one organic alcohol moiety may be polymeric and/orcomprise an aliphatic alcohol moiety, an aromatic or α-methyl aromaticalcohol moiety, or specifically an optionally substituted benzylicalcohol moiety.

In some embodiments, the methods may be used to prepare a range ofsynthons, which are useful in a range of downstream transformations,including the preparation of catechols (or other dihydroxylated aryl orheteroaryl moieties), ortho-alkenylated phenol (or other alkenylated 5-and 6-membered heteroaryl hydroxy moieties), ortho-carboxylic acidphenols (or other carboxylated 5- and 6-membered heteroaryl hydroxymoieties). Other of the methods provide for a range of dioxasilolanederivatives, which are useful as aryl transfer reagents (includingreacting with aromatic halides, such as bromides or iodides, to formbiaromatic product or aminating benzimidazoles) and for preparingbeta-aromatic substituted C₁₋₆ propionate ester products. A range ofspecific hydrosilane/alcohol combinations are disclosed herein, as arethe downstream transformations, each of which is considered anindependent embodiment of the present invention.

Those compositions associated with the methods and transformationsdescribed herein are also considered independent embodiments within thescope of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods, processes, devices, and systemsdisclosed. In addition, the drawings are not necessarily drawn to scale.In the drawings:

FIG. 1 illustrates various strategies for preparing silyl ethers.

FIG. 2 provides an exemplary overview of the substrates consideredwithin the scope of the present invention.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention is founded on a set of reactions, each of whichrelies on simple mixtures of hydrosilanes and uncomplexed potassiumhydroxide and sodium hydroxide, which together form in situ systems (thestructure and nature of the active species is still unknown) able todehydrogenative couple hydrosilanes and alcohols, and when combined, doso. Such transformations proceed without the required presence oftransition metal catalysts, superbases, fluoride ion, UV radiation orelectrical (including plasma) discharges. These reactions are relevantas an important advance in developing practical methods for thepreparation of products important for agrochemical, electronics, finechemicals, and pharmaceutical applications. They provide an importantsynthetic tool with respect to alcohol protection and directingstrategies. Importantly this reaction is of further interest since itproduces only environmentally benign silicates as the byproduct and canavoid metal waste streams or the use of harsh chemical catalysts. Theremarkable facility exhibited by these systems provides a useful tool inthe kit of chemists in these fields. Again, this utility can beleveraged when combined with other follow-on reactions.

The present invention may be understood more readily by reference to thefollowing description taken in connection with the accompanying Figuresand Examples, all of which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific products,methods, conditions or parameters described or shown herein, and thatthe terminology used herein is for the purpose of describing particularembodiments by way of example only and is not intended to be limiting ofany claimed invention. Similarly, unless specifically otherwise stated,any description as to a possible mechanism or mode of action or reasonfor improvement is meant to be illustrative only, and the inventionherein is not to be constrained by the correctness or incorrectness ofany such suggested mechanism or mode of action or reason forimprovement. Throughout this text, it is recognized that thedescriptions refer to both the compositions and methods of making andusing said compositions. That is, where the disclosure describes orclaims a feature or embodiment associated with a composition or a methodof making or using a composition, it is appreciated that such adescription or claim is intended to attribute these features orembodiment to embodiments in each of these contexts (i.e., compositions,methods of making, and methods of using).

Methods of Dehydrogenatively Coupling Hydrosilanes and Alcohols

The present invention includes embodiments related to methods fordehydrogenatively coupling hydrosilanes and alcohols (or otherhydroxy-containing materials, including inorganic materials), theirrelated compositions, and methods of using the derived products.

Some embodiments provides methods comprising contacting an organicsubstrate having at least one organic alcohol moiety with a mixture ofat least one hydrosilane and a sodium and/or potassium hydroxide, thecontacting resulting in the formation of a dehydrogenatively coupledsilyl ether. The use of NaOH, KOH, or a mixture thereof are consideredindependent embodiments of these methods. While throughout thisdisclosure, the invention is described in terms of organic substrates,it is important also to note that the methods and compositions are alsodirected to embodiments in which the substrate is or comprises aninorganic substrate, such as a hydrated oxide (e.g., of alumina, silica,titania, or zirconia, including hydroxylated aluminum, silicon,titanium, or zirconium surfaces) or water. In the former case, theproduct is a silylated inorganic surface; in the latter case, theproduct is a siloxane. The ability to append polysilanes onto hydratedinorganic oxides is especially valuable given the importance of Si—Sioligomers and polymers in materials science applications, as describedin Fujiki, M. Polymer Journal 2003, 35, 297-344, this reference beingincorporated by reference at least for its teaching of the methods ofpreparing and uses of such systems. Additionally, the reaction ofdiethylsilane with water under NaOH catalysis resulted in the formationof cyclic siloxanes, with trisiloxane being the major product by GC-MSanalysis. These products are precursors to valuable polysiloxanes, asdescribed for example in M. J. Hunter, et al., J Am. Chem. Soc., 1946,68, 667-672. This reference is also incorporated by reference at leastfor its teaching of the methods of preparing and uses of such systems.

Base-catalyzed methods for the formation of O—Si bonds bydehydrocoupling have been investigated by others, but not under thereactions conditions considered in the present disclosure. Indeed, theuse of simple base catalysts of the present invention are practicallyconvenient and robust. In stark contrast, the catalysts previously usedhave tended to be highly basic, for example, using hydrides, alkoxides,and transition metal hydrides, with or without n-butyl lithium (the term“superbase” is used herein to describe these stronger bases). See, e.g.,A, Weickgennant, et al., Chem. Asian J. 2009, 4, 406-410.) and A.Grajewska, et al., Synlett, 2010, 16, 2482-2484. Aside from thechallenges of working with these highly reactive materials, thesemethods do not have the scope and/or practical convenience/cost benefitsof the methods disclosed here. Silylation of alcohols by hydrosilanes ordisilanes have also been facilitated by fluoride ion (as tetrabutylammonium fluoride). Potassium hydroxide has been previously used, buteven here, the reactions conditions required the use of costly additivessuch as crown-ethers for activation. See, e.g., F. Le Bideau, et al.,Chem. Commun. 2001, 1408-1409. Consequently, the resultant scope ofprevious reports have been modest: phenols are notably absent, as ismonosilylation with dihydrosilanes, and very few functional groups ofvalue in downstream modification are described.

In the present disclosure, it is shown that the use of a milder basiccatalyst may greatly improve the scope of the reaction compared toprevious methods such as allowing reactions with phenols anddihydrosilanes and could potentially tolerate valuable and sensitivefunctional groups on the alcohol substrate and on the hydrosilane.Furthermore, using a less sterically demanding base catalyst allows forthe introduction of bulkier hydrosilane coupling partners, enabling thecatalytic silylene protection of 1,2-diols, which can be otherwisechallenging by both stoichiometric and catalytic means. The presentmethods provide a practical, convenient, and generalcross-dehydrogenative O—Si bond construction protocol, enabled by alkalimetal hydroxide-catalyzed Si—H/O—H bond coupling. The catalysts, NaOHand KOH, in the absence of crown ether activators, exhibit theattributes of (a) high functional group compatibility and mild basicity'(b) minimal steric demand to satisfy sterically demanding hydrosilanesand alcohol substrates; (c) ability to catalyze the dehydrocouplingreaction under mild conditions, and (d) have low toxicity and goodtolerance to ambient conditions. The specific nature of the K⁺ andespecially Na⁺ in the present systems appears to confer at least some ofthe benefits to the methods and systems.

The methods operate well in the complete or substantial absence oftransition metal ions, compounds, or catalysts. As used herein, unlessotherwise stated, the term “substantial absence” refers to the absenceof deliberately added material, in this case of transition metalcatalysts known to be or suspected of being operable in suchdehydrogenative coupling reactions. Where otherwise specified, the termmay also refer to the presence of the material at or below a certainthreshold levels described elsewhere herein. In certain embodiments, themethods are conducted in the substantial absence of transition metalions or catalysts. In other embodiments, the methods are conducted withless than 1000 ppm, 100 ppm, 50 ppm, or 10 ppm, based on the totalweight of the system.

Likewise, these methods are also operable in the absence orsubstantially complete absence of other electromagnetic or thermaltriggers needed for initiation or propagation. That is, theseembodiments do not need or use UV irradiation or electric or plasmadischarge conditions to operate.

In other embodiments, the methods are conducted in the substantialabsence of “superbases,” such as alkoxides, hydrides, alkyl lithiumreagents, or any chemical known to enhance the activity of the NaOH orKOH (e.g., crown ethers). Specifically in the case of NaOH or KOH,unless otherwise explicitly specified, the use of NaOH or KOH refers tocompositions or methods in which the systems which are completely orsubstantially devoid of crown ethers, cryptands, polyoxy- orpolyamino-ligands, ionophores, or other alkali metal chelating agentswhich are known to chelate the Na⁺ or K⁺ cations. While otherembodiments allow for their selective presence, as a general feature,the methods and systems avoid the use of these materials. In otherembodiments, the methods are conducted in the complete or substantialabsence of fluoride ion (which may be present as tetraalkyl ammoniumfluoride, for example).

Within the scope of the disclosure, there are few limits placed on thenature of the hydrosilane reagents, at least in the sense that these maybe individual discrete compounds, may be part of oligomeric or polymericstructures, or may be tethered to insoluble or sparingly soluble supportmedia for ease of work-up. That said, the hydrosilanes used in thepresent work are conveniently presented as soluble or at least simplecompounds,

In certain embodiments, the hydrosilane has a structure of Formula (I)or of Formula (II):

(R)_(3-m)Si(H)_(m+1)  (I)

(R)_(2-m)(H)_(m+1)Si—Si(R)_(3-m)(H)_(m)  (II)

where: m is independently 0, 1, or 2; and each R is independentlyoptionally substituted C₁₋₂₄ alkyl or heteroalkyl, optionallysubstituted C₂₋₂₄ alkenyl or heteroalkenyl, optionally substituted C₂₋₂₄alkynyl or heteroalkynyl, optionally substituted 6 to 18 ring memberedaryl or 5 to 18 ring membered heteroaryl, optionally substituted 6 to 18ring-membered alkaryl or 5 to 18 ring-membered heteroalkaryl, optionallysubstituted 6 to 18 ring-membered aralkyl or 5 to 18 ring-memberedheteroaralkyl, optionally substituted —O—C₁₋₂₄ alkyl or heteroalkyl,optionally substituted 6 to 18 ring-membered aryloxy or 5 to 18ring-membered heteroaryloxy, optionally substituted 6 to 18ring-membered alkaryloxy or 5 to 18 ring-membered heteroalkaryloxy, oroptionally substituted 6 to 18 ring-membered aralkoxy or 5 to 18ring-membered heteroaralkoxy, and, if substituted, the substituents maybe phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C₁-C₂₀alkylsulfanyl, C₅-C₂₀ arylsulfanyl, C₁-C₂₀ alkylsulfonyl, C₅-C₂₀arylsulfonyl, C₁-C₂₀ alkylsulfinyl, 5 to 12 ring-membered arylsulfinyl,sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C₁-C₂₀alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl,carboxyl, carboxylato, mercapto, formyl, C₁-C₂₀ thioester, cyano,cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy,styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, orhalogen, or a metal-containing or metalloid-containing group, where themetalloid is Sn or Ge, where the substituents may optionally provide atether to an insoluble or sparingly soluble support media comprisingalumina, silica, or carbon. In individual embodiments, m is 0, m is 1, mis 2. Each of the compounds of Formula (I) and Formula (II) representindependent embodiments.

In other embodiments, the hydrosilane is (R)₃SiH, (R)₂SiH₂, or (R)SiH₃,where R is independently C₁₋₆alkoxy, C₁₋₆alkyl, C₂₋₆alkenyl, C₆₋₂₄aryl,C₇₋₂₅aryloxy, a 5- or 6-ring membered heteroaryl, aralkyl, orheteroaralkyl compound or moiety. These substituents may be substitutedor unsubstituted, the optional substituents being described elsewhereherein. In certain specific embodiments, the hydrosilane is a compoundof Formula (I), where m is 1; in others, the hydrosilane is a compoundof Formula (I), where m is 2. In other embodiments, the hydrosilane isEtMe₂SiH, Et₃SiH, (n-Bu)₃SiH, (i-Pr)₃SiH, Et₂SiH₂, Ph₂MeSiH,(t-Bu)Me₂SiH, (t-Bu)₂SiH₂, PhMeSiH₂, PhMe₂SiH, BnMe₂SiH, (EtO)₃SiH,Me₂(pyridinyl)SiH, (i-Pr)₂(pyridinyl)SiH, Me₃Si—SiMe₂H, or any of thehydrosilanes exemplified in the Examples.

One of the many important features of the present invention is the widerange of alcohols that can be used in the present methods. The methodsare expected to be operable using mono-alcohols, diols, triols, polyols,sugars, polyhydridic alcohols (including so-called sugar alcohols, suchas arabitol, erythritol, glycerol, mannitol, sorbitol, and xylitol) andoligomers and polymers comprising one or more alcohol moieties. Incertain embodiment, for example, the organic substrate having at leastone organic alcohol moiety has a structure of Formula (IIIA):

R¹—OH  (IIIA)

where R¹ comprises an optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₂₋₂₄ alkenyl, optionally substituted C₂₋₂₄ alkynyl,optionally substituted C₆₋₂₄ aryl, optionally substituted C₁₋₂₄heteroalkyl, optionally substituted 5- or 6-ring membered heteroaryl,optionally substituted C₇₋₂₄ aralkyl, optionally substitutedheteroaralkyl, or optionally substituted metallocene. In otherembodiments, the organic substrate has a structure of Formula (IIIB):

HO—R²—OH  (IIIB),

where R² comprises an optionally substituted C₂₋₁₂ alkylene, optionallysubstituted C₂₋₁₂ alkenylene, optionally substituted C₆₋₂₄ arylene,optionally substituted C₁₋₁₂ heteroalkylene, or an optionallysubstituted 5- or 6-ring membered heteroarylene. In both cases, theoptional substituents are described elsewhere herein for thesesubstituents. In the case of the diols, In certain, the organicsubstrate having at least one organic alcohol moiety can comprise anoptionally substituted catechol, an optionally substitutedneopentyl-diol an optionally substituted pinacol, or a homolog thereof.

In more general embodiments, the organic substrate having at least oneorganic alcohol moiety is or comprises an optionally substitutedcatechol moiety or has a Formula (IV):

wherein n is from 0 to 6, preferably 0 or 1;

R^(M) and R^(N) are independently H or methyl

R^(D), R^(E), R^(F), and R^(G) are independently H, C₁₋₆ alkyl,optionally substituted phenyl, optionally substituted benzyl, optionallysubstituted 5- or 6-ring membered heteroaryl, wherein the optionalsubstituents are as described elsewhere herein, preferably C₁₋₃ alkyl,C₁₋₃ alkoxy, or halo. In certain of these embodiments, the organicsubstrate include substituted 1,2-diols, 1,3-diols, 1,4-diols, thesebeing substituted with one or more alkyl (including methyl) and/or aryl(including optionally substituted aryl or heteroaryl. Depending on thesubstituents, the diols may be chiral or achiral, and those comprisingchiral and achiral are considered independent embodiments within thescope of the present disclosure. For example:

As should be apparent to the skilled person, the terms 1,2-, 1,3-, and1,4-diols refer to the relative positions of the diols with respect toone another, not necessarily with respect to a specific position on thecarbon chain—see, e.g., the pinacol structure above may be considered a1,2-diol, even though the diols are in the 2,3-positions.

Again, the organic substrate may be polymeric, containing one or morealcohol moieties in the polymer chain; e.g., polyvinyl alcohol,polyalkylene glycol, and vinyl alcohol copolymers (e.g., ethylene/vinylalcohol copolymer). As shown in the Examples, in some embodiments, theat least one organic alcohol moiety comprises an alcohol having anorganic framework comprising aliphatic, olefinic, acetylenic, cyclic,heterocyclic, or aromatic features. The methods also well tolerate thevarious functional groups as described as substituents herein(including, e.g., amides, esters, epoxides and other cyclic ethers,strained rings, etc.). In independent embodiments, the organic alcoholmoiety may be bound to a primary, secondary, or tertiary carbon. Anotherof the attractive features of the present methods are the ability toform silyl ethers even with sterically crowded tertiary alcohols, forexample, adamantol. The at least one organic alcohol moiety may alsocomprise an aromatic alcohol moiety, e.g., a phenol, naphthol,pyridinol, furanol, thiophenol, etc., or an α-methyl aromatic moiety,e.g., benzyl alcohol, pyridinyl-methanol, furanyl-methanol,thiophenyl-methanol, etc.

The Examples provide exemplary reaction conditions useful for affectingthe desired transformations. In some embodiments, the conditionssufficient to silylate the organic substrate comprise heating theingredients at a temperature in a range of about 10° C. to about 100° C.In some cases, the methods may be conducted with the reagents at atemperature defined by one or more of the ranges of from about 10° C. to20° C., from 20° C. to 30° C., from 30° C. to 40° C., from 40° C. to 50°C., from 50° C. to 60° C., from 60° C. to 70° C., from 70° C. to 80° C.,from 80° C. to 90° C., from 90° C. to 200° C., or higher. Any of thetemperatures described in the Examples may be considered independentembodiments. Typical operating reaction times may range from about 2hours, from about 4 hours, from about 6 hours, or from about 10 hours toabout 28 days, to about 14 days, to about 7 days, to about 4 days, toabout 3 days, to about 48 hours, to about 24 hours, to about 12 hours,or to about 6 hours. The methods may employ lesser or longer times aswell.

These methods have been demonstrated using polar aprotic solvents,though other solvents may also be considered. Tetrahydrofuran,1,2-dimethoxyethane, and dimethyl formamide have been shown to workespecially well, but other polar aprotic solvents such as acetonitrile,dimethylacetamide (DMA), dimethyl formamide (DMF), dimethylsulfoxide,glycols and polyglycols (including, for example, dimethoxyethane, DME),optionally substituted dioxanes, dialkyl ethers (e.g., diethyl, dimethylether), hexamethylphosphoramide (HMPA), optionally substitutedtetrahydrofurans (including 2-methyltetrahydrofuran) and furans, andN-methylpyrrolidone (NMP) are also expected to work well.

Downstream Reactions Using the Products of the Instant Disclosure

Once formed, the products of the disclosed methods can be used asconvenient precursors to a range of “downstream” reactions (i.e.,reactions to be applied subsequent to the disclosed coupling reactions),depending on the nature of the product. In certain embodiments, thevarious reactions may be done in so-called “one pot” conditions; inother embodiments, the coupled silyl ethers are isolated, and optionallypurified, before progressing the downstream reactions. The presentdisclosure contemplates that methods employing these known methods, whencoupled with the inventive methods described here, are within the scopeof the present disclosure.

Given the flexibility of the methods, depending on the nature ofhydrosilanes (for example, the size/bulk of the substituents) andalcohol precursors (as described above), a large array of products canbe prepared, many of which are useful for downstream reactions. TheExamples section provides a good overview of the types of manipulationsavailable to the present method. In some cases, aside from the simplerchemistries, the present methods allows for the easy preparation ofmaterials otherwise difficult to make or unaccessible by other means.

In one example of this flexibility, the reactivity of dihydrosilanes,R₂SiH₂, depends on the nature/bulk of the associated R-groups, as wellas the relative hydrosilane/alcohol stoichiometry. Using bulky tertiarygroups, such as tert-butyl, 2-methyl-butan-2-ol, or otheralkyl-C(CH₃)₂—OH alcohols, as the substituents on the hydrosilanes (asin (tert-butyl)₂Si(H)₂), the resulting product is the correspondingsimple hydrosilyl ether (less bulky dihydrosilanes tend to providebridging silyl diethers—i.e., dialkoxysilanes—by doubledehydrocoupling). See Examples 2.2.6 and 2.2.28 and compare Example2.2.9. While many of the descriptions which follow are provided for thesilylation of benzyl alcohol and phenol, respectively, it should bereadily apparent that other mono-alcohols, including aryl or heteroarylalcohols, would be similarly silylated to form the correspondingdi-tert-butyl-hydrosilyl ether.

(V-B) (VI-B)

where (Het)aryl represents any phenyl, naphthyl, or 5- or 6-memberedheteroaryl moiety. In one example of this class, where (Het)aryl is anoptionally substituted phenyl, such a reaction may be representedschematically as:

This example is presented here reflecting a phenol precursor, but againit is to be appreciated that an optionally substituted naphthol orhydroxylated 5- or 6-membered heteroaryl moiety may stand in the placeof the phenyl ring of the phenol. In this regard, the followingdescriptions, while presented in the context of phenol chemistry, isexpected to be operable as described for other aromatic (aryl andheteroaryl (Het(aryl))) alcohols, including, but not limited to thosealcohols where Het(aryl) is or comprises a furan, pyrrole, thiophene,pyrazole, imidazole, triazole, isoxazole, oxazole, thiazole,isothiazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine,triazone, benzofuran, benzopyrrole, benzothiophene, isobenzofuran,isobenzopyrrole, isobenzothiophene, indole, isoindole, indolizine,indazole, azaindole, benzisoxazole, benzoxazole, quinoline,isoquinoline, cinnoline, quinazoline, naphthyridine,2,3-dihydrobenzofuran, 2,3-dihydrobenzopyrrole,2,3-dihydrobenzothiophene, dibenzofuran, xanthene, dibenzopyrol, ordibenzothiophene compound or moiety. Likewise, while this example isgiven using di-tert-butyl-dihydro-silane, it is also to be appreciatedthat other bulky substituents, for example tertiary alkyl groups, may beused instead of the tert-butyl groups. The following descriptions, then,while presented in the context of di-tert-butyl-dihydro-silanechemistry, is expected to be operable as described for otherdihydrosilanes having similarly bulky substituents.

Within this framework, where at least one organic alcohol moiety is anoptionally substituted phenol and the at least one hydrosilane is(tert-butyl)₂Si(H)₂, the reaction product comprising a di-tert-butylsilyl phenyl ether. Again, any hydroxylated naphthalene or 5- or6-membered heteroaryl moiety made stand in place of the phenol and anybulky dihydrosilane may stand in the place of (tert-butyl)₂Si(H)₂.Without intending to limit the definition of the substitution on thephenol (or other aromatic), in certain embodiments, the phenol (or otheraromatic) may be substituted as described in the structure of Formula(V), where n is 0, 1, 2, 3, 5, or 5, and R^(A) is optionally at leastone of aldehyde (—CHO), C₁₋₆ alkyl, C₁₋₆ alkylcarbonyl(—C(O)—C₁₋₆alkyl), C₁₋₆ alkoxy, C₁₋₆ alkoxycarbonyl (—C(O)—C₁₋₆alkyl),—C(O)—C₆₋₂₄ aryl), —C(O)-(5- or 6 membered heteroaryl), halo, nitrile,or nitro. In other embodiments, n is 2, and two R^(A)'s together withthe phenyl ring form a fused 5- or 6 membered carbocyclic ring or 5- or6 membered mono- or diether ring, e.g.,

Such a reactions may be represented schematically as:

In further embodiments, the aromatic silyl ether (as exemplified bydi-tert-butyl silyl phenyl ether) may be converted to a correspondingaromatic hydroxy silyl ether (e.g., di-tert-butyl hydroxy silyl phenylether). In certain aspects, this step comprises contacting the aromaticsilyl ether with a base (e.g., hydroxide base) to form an aromatichydroxy silyl ether. Without intending to limit the definition of thesubstitution of the substrates, in certain embodiments, the aromaticsilyl ether has a structure of Formula (VI), or a correspondingstructure for other aromatic analogs, where n is 0, 1, 2, 3, 5, or 5,and R^(A) are described as elsewhere herein and the aromatic hydroxysilyl ether corresponding to Formula (VII) is correspondinglysubstituted. In certain of these embodiments, the base comprises a formof hydroxide, such as aqueous carbonate or basic (hydroxide-containing)DMF, as described for example in Huang, J. Am. Chem. Soc., 2011, 133(44), 17630-17633. Such a reaction may be represented schematically as:

An overall exemplary transformation may be represented by the schematic:

The phenyl version of this aromatic hydroxy silyl ether has been shownto be a useful intermediate for a range of reactions, some of which aredescribed as follows, and it is expected that the corresponding aromaticanalogs are equally useful.

In some embodiments, the aromatic hydroxy silyl ether (as exemplified bydi-tert-butyl hydroxy silyl phenyl ether) can be converted to a1,2-dihydroxy aromatic moiety (for example, catechol as derived from thephenol derivative). In some embodiments, this step comprises furthercontacting the aromatic hydroxy silyl ether (as exemplified bydi-tert-butyl hydroxy silyl phenyl ether) with an acetoxylating reagentin the presence of a palladium catalyst to form to the 1,2-dihydroxyaromatic moiety (for example, catechol as derived from the phenolderivative). Again, without intending to limit the definition of thesubstitution of the substrates, in certain embodiments, the aromaticsilyl ether has a structure of Formula (VII), or a correspondingstructure for other aromatic analogs, where n is 0, 1, 2, 3, 5, or 5,and R^(A) are described as elsewhere herein, and the correspondingcatechol (or other aromatic 1,2-diol) of Formula (IX) is correspondinglysubstituted. In certain of these embodiments, the acetoxylating reagentis or comprises PhI(OAc)₂ and the palladium catalyst comprises adicarboxylate of palladium (II). In the reactions described herein ascomprising a dicarboxylate of palladium (II) (or copper carboxylate, asdiscussed below), the carboxylate can be any alkyl or aryl carboxylate,though typically in such reactions, acetates, benzoates, or pivalatesare used. These reactions are analogous to those described in Huang, J.Am. Chem. Soc., 2011, 133 (44), 17630-17633, which describes thistransformation as a highly site-selective silanol-directed, Pd-catalyzedC—H oxygenation of phenols into catechols that operates via asilanol-directed acetoxylation, followed by a subsequent acid-catalyzedcyclization reaction into a cyclic silicon-protected catechol. Thedesilylation of the silacyle with TBAF to uncover the catechol productis described as routine. Exemplary reaction conditions in this referenceincludes reacting the 3-methyl derivative of the compound of Formula(VII) with Pd(OPiv)₂ (5 mol %), PhI(OAc)₂ (2 eq) in toluene at 100° C.,for 6-12 hrs., followed by reaction with TBAF in THF. Such a reactionmay be represented schematically as:

In other embodiments, the aromatic hydroxy silyl ether (as exemplifiedby di-tert-butyl hydroxy silyl phenyl ether) can be converted to anortho-alkenylated aromatic alcohol (e.g., an ortho-alkenylated phenol).In some embodiments, this step comprises further contacting the aromatichydroxy silyl ether (as exemplified by di-tert-butyl hydroxy silylphenyl ether) with a terminal olefin in the presence of a palladiumcatalyst to form the ortho-alkenylated product. Again, without intendingto limit the definition of the substitution of the substrates, incertain embodiments the terminal olefin has a structure comprisingFormula (X):

where R^(B) is H or C₁₋₁₂ alkyl and R^(C) is aldehyde, —C(O)—C₁₋₁₂alkyl, —C(O)—OC₁₋₁₂ alkyl, —S(O)₂—C₁₋₁₂ alkyl, —S(O)₂—C₆₋₂₄ aryl,—S(O)₂—OC₁₋₁₂ alkyl, —S(O)₂—OC₆₋₂₄ aryl, optionally substituted (withone or more halo or C₁₋₆ alkyl) phenyl, or an optionally substituted 5-or 6-membered heterocyclic group.

In some independent embodiments, the aromatic hydroxy silyl ether has astructure corresponding to the compound of Formula (VII), theortho-alkenylated product has a structure corresponding to the compoundof Formula (XI), where n is 0, 1, 2, 3, 5, or 5, and R^(A) are describedelsewhere herein, and the corresponding ortho-alkenylated product iscorrespondingly substituted. In certain of these embodiments, thepalladium catalyst comprises a dicarboxylate of palladium (II) asdescribed above. For phenols, C. Huang, et al., J Am. Chem. Soc., 2011,133 (32), pp 12406-12409 describes this transformation assilanol-directed, Pd(II)-catalyzed ortho-C—H alkenylation of phenols.Exemplary reaction conditions in this reference includes reacting the3,4-dimethyl derivative of the compound of Formula (VII) with a varietyof functionalized terminal olefins (2-4 equiv) in the presence ofPd(OAC)₂ (10 mol %), (+)menthyl(O₂C)-Leu-OH (20 mol %)), Li₂CO₃ (1equiv), and AgOAc (4 equiv), in C₆F₆ at 100° C., followed by routinedesilylation using TBAF/THF. Such a reaction may be representedschematically as:

In sill other embodiments, the aromatic hydroxy silyl ether (again, asexemplified by di-tert-butyl hydroxy silyl phenyl ether) can beconverted to an ortho-carboxylic acid aromatic alcohol. In certainaspects of these embodiments, this step further comprises contacting thearomatic hydroxy silyl ether with carbon monoxide (CO) in the presenceof a palladium catalyst to form an ortho-carboxylic acid phenol. Each ofthe hydroxy and carboxy functional groups may be further functionalizedby any means suitable for those functional groups. Again, withoutintending to limit the definition of the substitution of the substrates,in certain embodiments, the aromatic silyl ether has a structure ofFormula (VII), or a corresponding structure for other aromatic analogs,where n is 0, 1, 2, 3, 5, or 5, and R^(A) are described as elsewhereherein, and the corresponding ortho-carboxylic acid alcohol (asexemplified in Formula (XIII) is correspondingly substituted. Thistransformation for the phenol derivative is described in Y. Wang, etal., Angew Chem Int Ed Engl. 2015 Feb. 9; 54(7): 2255-2259. Exemplaryreaction conditions in this reference includes reacting the 3-tert-butylderivative of the compound of Formula (VII) with CO in the presence ofPd(OAC)₂ (10 mol %), Boc-Leu-OH (20 mol %)), AgOAc (3 equiv), andCF₃CH₂OH (3 equiv) in dichloroethane at 95° C. for 18 hours, to form thecyclic derivative corresponding to Formula (XII), followed by routinedesilylation using TBAF/THF to form the salicyclic derivative (Formula(XIII)). Such a reaction may be represented schematically as:

As described in another section and exemplified herein, the reaction ofdihydrosilanes with diols (or polyols) provides entry into another classof cyclic dioxasilolane derivatives, and as shown in the Examples, suchchemistries can afford useful synthons for a range of chemicaltransformations. As such, further embodiments include those where theproducts derived by the inventive methods discussed herein are furthersubjected to conditions conducive to these downstream transformations.Some of these are described as follows.

In some embodiments, the dihydrosilane may be described in terms of astructure (R^(J))(R^(K))Si(H)₂, where R^(J) comprises an optionallysubstituted phenyl, optionally substituted naphthyl, or optionallysubstituted 5- or 6-membered heteroaryl moiety and where R^(K) is a C₁₋₃alkyl. More broadly, R^(J) represents a moiety suitable for transfer toa suitable substrate when the corresponding cyclic dioxasilolane is usedfor that application (for example, the definition of R^(J) may furtherinclude allyl) and R^(K) is not.

In some embodiments, then R^(K) is methyl. In other independentembodiments, the organic substrate having at least one organic alcoholmoiety is a compound of Formula (IIIB) as described above, or a compoundof structure (IV)

the product of the reaction comprising a cyclic dioxasilolane. Incertain Aspects of this Embodiment, the product cyclic dioxasilolane hasa structure of Formula (XV);

wherein n is from 0 to 6; and

R^(D), R^(E), R^(F), and R^(G) are independently H, C₁₋₆ alkyl,optionally substituted phenyl, optionally substituted benzyl, optionallysubstituted 5- or 6-ring membered heteroaryl, wherein the optionalsubstituents are described elsewhere. In some embodiments, the optionalsubstituents are C₁₋₃ alkyl, C₁₋₃ alkoxy, or halo. The reaction may berepresented schematically as:

Where R^(K) is methyl, this becomes:

In some embodiments, R^(J) comprises an optionally substituted phenyl.In other embodiments, the organic substrate having at least one organicalcohol moiety is optionally substituted 3-phenyl-butane-1,3-diol,2,2-dimethyl-propane-1,3-diol, catechol, or pinacol. Without intendingto necessarily limit the substituent pattern on the optionallysubstituted phenyl, in some embodiments, the structures of Formula (XIV)may be characterized as having the structure of Formula (XIV-A) and theproduct of the method as having a structure of any one of Formulae(XV-A), (XV-A1), (XV-A2), or (XV-A3), where (R^(A))_(n) is definedelsewhere herein.

Any of the cyclic dioxasilolanes described herein by the formula(R^(J))(R^(K))Si(H)₂, whether prepared by the inventive methods orotherwise, may further be used in palladium catalyzed coupling reactionsto form biaromatic compounds. In certain embodiments, these cyclicdioxasilolanes, for example as represented by the compound of Formula(XV) may be contacted with an aromatic bromide or iodide in the presenceof a palladium catalyst under conditions sufficient to couple thearomatic R^(J) moiety to the aromatic bromide or iodide to form abiaromatic product. In this context, the representation of Formula (XV)independently embodies any of the subgenera or specific compoundsencompassed by this structure:

Similar reactions using disiloxane precursors (and not the cyclicdioxasilolanes of the instant invention) are described in C. Cheng andJ. F. Hartwig, Science, 343 (6173), 853-857 (2014). Exemplary reactionconditions in this reference include the reaction of (phenyl)SiMe(OTMS)₂with PhBr or 3-iodoanisole (0.7 to 1.5 equiv), KOTMS (3 equiv), Pd(OAc)₂(0.05 equiv), dcpe (1,2-bis(dicyclohexylphosphino)ethane; 0.055 equiv),THF or toluene, 65 to 100° C., 5 to 14 hours.

Likewise, any of the cyclic dioxasilolanes described herein by theformula (R^(J))(R^(K))Si(H)₂, whether prepared by the inventive methodsor otherwise, may further be used in rhodium catalyzed couplingreactions to form beta-aromatic substituted C₁₋₆ propionate esterproducts:

For example, in some embodiments, the method comprises reacting thecompound of Formula (XV) with C₁₋₆ acrylate ester in the presence of arhodium catalyst under conditions sufficient to couple the aromaticR^(J) moiety with the C₁₋₆ acrylate ester to form a beta-aromaticsubstituted C₁₋₆ propionate ester product. Exemplary rhodium catalystsinclude [Rh(cyclooctadiene)Cl]₂ and [Rh(cyclooctene)₂Cl]₂. Suchreactions are described in C. Cheng and J. F. Hartwig, Science, 343(6173), 853-857 (2014). Exemplary reaction conditions include thereaction of (phenyl)SiMe(OTMS)₂ with tert-butyl acrylate (0.5 equiv),[Rh(cod)Cl]₂ (0.02 equiv), TBAF (3 equiv), THF, H₂O, 100° C., 14 hours.

Likewise, any of the cyclic dioxasilolanes described herein by theformula (R^(J))(R^(K))Si(H)₂, whether prepared by the inventive methodsor otherwise, may further be used to couple R^(J) with substitutedbenzimidazoles. In some embodiment, this involves the use of coppercatalysts. For example, in some embodiments, this reaction comprisesreacting the compound of Formula (XV) with an optionally substitutedbenzimidazole in the presence of a copper catalyst under conditionssufficient to aminate the benzimidazole with the aromatic R^(J) moiety.Exemplary copper catalysts include copper carboxylates, where thecarboxylates may include acetates, benzoates, and pivalates. Suchreactions are described in C. Cheng and J. F. Hartwig, Science, 343(6173), 853-857 (2014): Exemplary conditions are provided in thisreaction for the reaction of (phenyl)SiMe(OTMS)₂ with benzimidazole (0.5equiv), Cu(OAc)₂ (0.6 equiv), TBAF (1 equiv), dimethylformamide (DMF),23° C., 36 hours.

The references to C. Cheng and J. F. Hartwig, Science, 343 (6173),853-857 (2014), J. Am. Chem. Soc., 2011, 133 (32), pp 12406-12409,Huang, J. Am. Chem. Soc., 2011, 133 (44), 17630-17633, C. Huang, et al.,and Y. Wang, et al., Angew Chem Int Ed Engl. 2015 Feb. 9; 54(7):2255-2259 are incorporated by reference herein in their entireties, orat least for their teachings of the described transformations and thematerials and conditions used for the same.

Compositions

The inventive concepts have been thus far described in terms of themethods of dehydrogenatively decoupling hydrosilanes and alcohols toform silyl ethers. It should be appreciated that the products obtainedfrom such methods, to the extent that they are not practically availableby other means known at the time of this filing, and the composition orsystems used in these methods, are all considered within the scope ofthe present disclosure.

Again, the scope of the present disclosure includes embodiments for anycomposition used or generated in any of these inventive methods. Thesecompositions, in various embodiments, include the hydrosilanes,alcohols, sodium and/or potassium hydroxide, and optionally any of theproducts resulting from the reactions. For example, certain embodimentsprovide compositions comprising or consisting essentially of (a) atleast one hydrosilane; (b) sodium and/or potassium hydroxide; (c) anorganic substrate having at least one organic alcohol moiety; andoptionally (d) a silyl ether resulting from the dehydrogenative couplingof the at least one hydrosilane and the at least one alcohol moiety. Inother embodiments, the silyl ether resulting from the dehydrogenativecoupling is present. In still other embodiments, the compositionscomprise any of the aprotic polar solvents described as useful in theinventive methods.

As related to the compositions and methods, the term “consistingessentially of” refers compositions whose basic and novelcharacteristic(s) are those named ingredients necessary for the progressof the reaction, as defined herein, but which may also contain otheringredients which do not affect the progression of the reaction. Forexample, a composition consisting essentially of the four ingredients(a-d) might also contain a colorant, as such a material would not beexpected to have any effect on the progress of the inventive methods,but it would not contain, for example, transition metal catalysts, ions,or compounds, “superbases,” such as alkoxides, hydrides, alkyl lithiumreagents, or any chemical known to enhance the activity of the NaOH orKOH (e.g., crown ethers), and/or fluoride ion. While such materials areknown to promote such dehydrogenative coupling reactions as describedherein, they are not necessary or desirable in the present context, andin preferred embodiments, they are completely or substantially freethese materials.

In the context of these compositions, various embodiments include thosecompositions comprising any genus, species, or individual of thehydrosilane, alcohol, and silyl ether described herein, in anycombination or permutations. These include, but are not limited to, thehydrosilanes having a genus structure of Formulae (I), (II), (XIV),(XIV-A), (R^(J))(R^(K))Si(H)₂, or any subgenus or example thereof. Inother various embodiments, the compositions include one or more of thealcohols described herein as useful in the methods, including by notlimited to the substrates defined by the genus structures of Formulae(IIIA), (IIIB), (IV), (V), (V-A), (V-B) or any subgenus or examplethereof. In other various embodiments, the compositions include one ormore of the dehydrogenatively coupled silyl ethers described herein,including by not limited to the substrates defined by the genusstructures of Formulae (VI), (VI-A), (VI-B), (XV), (XV-A), (XV-A1),(XV-A2), or (XV-A3) or any subgenus or example thereof.

Terms

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art.

When a value is expressed as an approximation, for example by use of thedescriptor “about,” it will be understood that the particular valueforms another embodiment. In general, use of a term such as “about”indicates approximations that can vary depending on the desiredproperties sought to be obtained by the disclosed subject matter and isto be interpreted in the specific context in which it is used, based onits function. The person skilled in the art will be able to interpretthis as a matter of routine. In some cases, the number of significantfigures used for a particular value may be one non-limiting method ofdetermining the extent of the word “about.” In other cases, thegradations used in a series of values may be used to determine theintended range available to the term “about” for each value. Wherepresent, all ranges are inclusive and combinable. That is, references tovalues stated in ranges include every value within that range.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the invention that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. Finally, while anembodiment may be described as part of a series of steps or part of amore general structure, each said step may also be considered anindependent embodiment in itself, combinable with others. For example,where method steps are described as building from previous steps, it isintended that each individual step is an independent embodiment, withoutthe necessary use of the recited precursor step.

The transitional terms “comprising,” “consisting essentially of,” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method steps; (ii) “consisting of” excludes any element,step, or ingredient not specified in the claim; and (iii) “consistingessentially of” limits the scope of a claim to the specified materialsor steps and those that do not materially affect the basic and novelcharacteristic(s) of the claimed invention. Embodiments described interms of the phrase “comprising” (or its equivalents), also provide, asembodiments, those which are independently described in terms of“consisting of” and “consisting essentially of” For those embodimentsprovided in terms of “consisting essentially of,” the basic and novelcharacteristic(s) is the facile operability of the methods to providesilylated products at meaningful yields (or the ability of the systemsused in such methods to provide the product compositions at meaningfulyields or the compositions derived therefrom); i.e., todehydrogenatively couple hydrosilanes and alcohols to form silyl ethersusing only those ingredients listed. The term “consisting essentiallyof” has been further discussed elsewhere herein.

The term “meaningful product yields” is intended to reflect productyields of greater than 20%, but when specified, this term may also referto yields of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% or more,relative to the amount of original substrate.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C.” Similarly, a designation such as C₁₋₃ includes not onlyC₁₋₃, but also C₁, C₂, C₃, C₁₋₂, C₂₋₃, and C_(1,3), as separateembodiments.

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

The term “alkyl” as used herein refers to a linear, branched, or cyclicsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 24 carbon atoms, preferably 1 to about 12 carbonatoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, octyl, decyl, and the like, as well as cycloalkylgroups such as cyclopentyl, cyclohexyl and the like. Generally, althoughagain not necessarily, alkyl groups herein contain 1 to about 12 carbonatoms. The term also includes “lower alkyl” as separate embodiments,which refers to an alkyl group of 1 to 6 carbon atoms, and the specificterm “cycloalkyl” intends a cyclic alkyl group, typically having 4 to 8,preferably 5 to 7, carbon atoms. The term “substituted alkyl” refers toalkyl groups substituted with one or more substituent groups, and theterms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkylgroups in which at least one carbon atom is replaced with a heteroatom,for example providing at least one amino, ether, sulfide, sulfoxide,sulfone, phosphino, phosphate, or phosphite linkage. If not otherwiseindicated, the terms “alkyl” and “lower alkyl” include linear, branched,cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyland lower alkyl groups, respectively.

The term “alkylene” as used herein refers to a difunctional linear,branched, or cyclic alkyl group, where “alkyl” is as defined above.

The term “alkenyl” as used herein refers to a linear, branched, orcyclic hydrocarbon group of 2 to about 24 carbon atoms containing atleast one double bond, such as ethenyl, n-propenyl, isopropenyl,n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl,eicosenyl, tetracosenyl, and the like. Preferred alkenyl groups hereincontain 2 to about 12 carbon atoms. The term also includes “loweralkenyl” as separate embodiments, which refers to an alkenyl group of 2to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclicalkenyl group, preferably having 5 to 8 carbon atoms. The term“substituted alkenyl” refers to alkenyl groups substituted with one ormore substituent groups, and the terms “heteroatom-containing alkenyl”and “heteroalkenyl” refer to alkenyl groups in which at least one carbonatom is replaced with a heteroatom, as described above for “alkyl.” Ifnot otherwise indicated, the terms “alkenyl” and “lower alkenyl” includelinear, branched, cyclic, unsubstituted, substituted, and/orheteroatom-containing alkenyl and lower alkenyl groups, respectively.

The term “alkenylene” as used herein refers to a difunctional linear,branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

The term “alkynyl” as used herein refers to a linear or branchedhydrocarbon group of 2 to about 24 carbon atoms containing at least onetriple bond, such as ethynyl, n-propynyl, and the like. Preferredalkynyl groups herein contain 2 to about 12 carbon atoms. The term“lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms. Theterm also includes “lower alkynyl” as separate embodiments, which refersto an alkynyl group substituted with one or more substituent groups, andthe terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer toalkynyl in which at least one carbon atom is replaced with a heteroatom.If not otherwise indicated, the terms “alkynyl” and “lower alkynyl”include a linear, branched, unsubstituted, substituted, and/orheteroatom-containing alkynyl and lower alkynyl group, respectively.

The term “alkoxy” as used herein intends an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group may berepresented as —O-alkyl where alkyl is as defined above. The term alsoincludes “lower alkoxy” as separate embodiments, which refers to analkoxy group containing 1 to 6 carbon atoms. Analogously, “alkenyloxy”and “lower alkenyloxy” respectively refer to an alkenyl and loweralkenyl group bound through a single, terminal ether linkage, and“alkynyloxy” and “lower alkynyloxy” respectively refer to an alkynyl andlower alkynyl group bound through a single, terminal ether linkage.

The term “aromatic” refers to the ring moieties which satisfy the Hückel4n+2 rule for aromaticity, and includes both aryl (i.e., carbocyclic)and heteroaryl (also called heteroaromatic) structures, including aryl,aralkyl, alkaryl, heteroaryl, heteroaralkyl, or alkheteroaryl moieties,or pre-polymeric (e.g., monomeric, dimeric), oligomeric or polymericanalogs thereof.

The term “aryl” as used herein, and unless otherwise specified, refersto a carbocyclic aromatic substituent or structure containing a singlearomatic ring or multiple aromatic rings that are fused together,directly linked, or indirectly linked (such that the different aromaticrings are bound to a common group such as a methylene or ethylenemoiety). Preferred aryl groups contain 6 to 24 carbon atoms, andparticularly preferred aryl groups contain 6 to 14 carbon atoms.Exemplary aryl groups contain one aromatic ring or two fused or linkedaromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether,diphenylamine, benzophenone, and the like. “Substituted aryl” refers toan aryl moiety substituted with one or more substituent groups, and theterms “heteroatom-containing aryl” and “heteroaryl” refer to arylsubstituents in which at least one carbon atom is replaced with aheteroatom, as will be described in further detail elsewhere herein.Exemplary embodiments of heteroaryl moieties or compounds include furan,pyrrole, thiophene, pyrazole, imidazole, triazole, isoxazole, oxazole,thiazole, isothiazole, oxadiazole, pyridine, pyridazine, pyrimidine,pyrazine, triazone, benzofuran, benzopyrrole, benzothiophene,isobenzofuran, isobenzopyrrole, isobenzothiophene, indole, isoindole,indolizine, indazole, azaindole, benzisoxazole, benzoxazole, quinoline,isoquinoline, cinnoline, quinazoline, naphthyridine,2,3-dihydrobenzofuran, 2,3-dihydrobenzopyrrole,2,3-dihydrobenzothiophene, dibenzofuran, xanthene, dibenzopyrol, ordibenzothiophene compound or moiety.

The term “aryloxy” as used herein refers to an aryl group bound througha single, terminal ether linkage, wherein “aryl” is as defined above. An“aryloxy” group may be represented as —O-aryl where aryl is as definedabove. Preferred aryloxy groups contain 6 to 24 carbon atoms, andparticularly preferred aryloxy groups contain 6 to 14 carbon atoms.Examples of aryloxy groups include, without limitation, phenoxy,o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy,m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy,3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent,and the term “aralkyl” refers to an alkyl group with an arylsubstituent, wherein “aryl” and “alkyl” are as defined above. Preferredalkaryl and aralkyl groups contain 7 to 24 carbon atoms, andparticularly preferred alkaryl and aralkyl groups contain 7 to 16 carbonatoms. Alkaryl groups include, for example, p-methylphenyl,2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl,7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like.Examples of aralkyl groups include, without limitation, benzyl,2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl,4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl,4-benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and“aralkyloxy” refer to substituents of the formula —OR wherein R isalkaryl or aralkyl, respectively, as just defined.

The term “acyl” refers to substituents having the formula —(CO)-alkyl,—(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers tosubstituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or—O(CO)-aralkyl, wherein “alkyl,” “aryl, and “aralkyl” are as definedabove.

The terms “cyclic” and “ring” refer to alicyclic or aromatic groups thatmay or may not be substituted and/or heteroatom-containing, and that maybe monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used inthe conventional sense to refer to an aliphatic cyclic moiety, asopposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic,or polycyclic. The term “acyclic” refers to a structure in which thedouble bond is not contained within a ring structure.

The terms “halo,” “halide,” and “halogen” are used in the conventionalsense to refer to a chloro, bromo, fluoro, or iodo substituent.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 toabout 30 carbon atoms, preferably 1 to about 24 carbon atoms, mostpreferably 1 to about 12 carbon atoms, including linear, branched,cyclic, saturated, and unsaturated species, such as alkyl groups,alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl”intends a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4carbon atoms, and the term “hydrocarbylene” intends a divalenthydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms,including linear, branched, cyclic, saturated and unsaturated species.The term “lower hydrocarbylene” intends a hydrocarbylene group of 1 to 6carbon atoms. “Substituted hydrocarbyl” refers to hydrocarbylsubstituted with one or more substituent groups, and the terms“heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer tohydrocarbyl in which at least one carbon atom is replaced with aheteroatom. Similarly, “substituted hydrocarbylene” refers tohydrocarbylene substituted with one or more substituent groups, and theterms “heteroatom-containing hydrocarbylene” and heterohydrocarbylene”refer to hydrocarbylene in which at least one carbon atom is replacedwith a heteroatom. Unless otherwise indicated, the term “hydrocarbyl”and “hydrocarbylene” are to be interpreted as including substitutedand/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties,respectively.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbylmolecular fragment in which one or more carbon atoms is replaced with anatom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus orsilicon, typically nitrogen, oxygen or sulfur. Similarly, the term“heteroalkyl” refers to an alkyl substituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the terms “heteroaryl” andheteroaromatic” respectively refer to “aryl” and “aromatic” substituentsthat are heteroatom-containing, and the like. It should be noted that a“heterocyclic” group or compound may or may not be aromatic, and furtherthat “heterocycles” may be monocyclic, bicyclic, or polycyclic asdescribed above with respect to the term “aryl.” Examples of heteroalkylgroups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylatedamino alkyl, and the like. Non-limiting examples of heteroarylsubstituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl,indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., andexamples of heteroatom-containing alicyclic groups are pyrrolidino,morpholino, piperazino, piperidino, etc.

As used herein, the terms “substrate” or “organic substrate” areintended to connote both discrete small molecules (sometimes describedas “organic compounds”) and oligomers and polymers containing analcoholic hydroxy group. The term “aromatic moieties” is intended torefer to those portions of the compounds, pre-polymers (i.e., monomericcompounds capable of polymerizing), oligomers, or polymers having atleast one of the indicated aromatic structures. Where shown asstructures, the moieties contain at least that which is shown, as wellas containing further functionalization, substituents, or both,including but not limited to the functionalization described as “Fn”herein.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,”“substituted aryl,” and the like, as alluded to in some of theaforementioned definitions, is meant that in the hydrocarbyl, alkyl,aryl, heteroaryl, or other moiety, at least one hydrogen atom bound to acarbon (or other) atom is replaced with one or more non-hydrogensubstituents. Examples of such substituents include, without limitation:functional groups referred to herein as “Fn,” such as halo (e.g., F, Cl,Br, I), hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄alkynyloxy, C₅-C₂₄ aryloxy, C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl(including C₁-C₂₄ alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl(—CO-aryl)), acyloxy (—O-acyl, including C₂-C₂₄ alkylcarbonyloxy(—O—CO-alkyl) and C₆-C₂₄ arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄alkoxycarbonyl ((CO)—O-alkyl), C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl),halocarbonyl (—CO)-X where X is halo), C₂-C₂₄ alkylcarbonato(—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato (—O—(CO)—O-aryl), carboxy(—COOH), carboxylato (—COO—), carbamoyl (—(CO)—NH₂), mono-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₁-C₂₄haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄ aryl)substitutedcarbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄aryl)-substituted carbamoyl, thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄alkyl)-substituted thiocarbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄alkyl)-substituted thiocarbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)substituted thiocarbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl, carbamido(—NH—(CO)—NH₂), cyano(-C≡N), cyanato (—O—C═N), thiocyanato (—S—C═N),formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂), mono-(C₁-C₂₄alkyl)-substituted amino, di-(C₁-C₂₄ alkyl)-substituted amino,mono-(C₅-C₂₄ aryl)substituted amino, di-(C₅-C₂₄ aryl)-substituted amino,C₁-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄ arylamido (—NH—(CO)-aryl),imino (—CR═NH where R=hydrogen, C₁-C₂₄ alkyl, C5-C24 aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), C₂-C₂₀ alkylimino (—CR═N(alkyl), whereR=hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl,etc.), arylimino (—CR═N(aryl), where R=hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), nitro (—NO₂), nitroso(—NO), sulfo (—SO₂OH), sulfonate(SO₂O—), C₁-C₂₄ alkylsulfanyl (—S-alkyl;also termed “alkylthio”), C₅-C₂₄ arylsulfanyl (—S-aryl; also termed“arylthio”), C₁-C₂₄ alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl(—(SO)-aryl), C₁-C₂₄ alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄monoalkylaminosulfonyl-SO₂—N(H) alkyl), C₁-C₂₄dialkylaminosulfonyl-SO₂—N(alkyl)₂, C₅-C₂₄ arylsulfonyl (—SO₂-aryl),boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂ where R is alkyl orother hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato (—P(O)(O)₂),phosphinato (P(O)(O—)), phospho (—PO₂), and phosphine (—PH₂); and thehydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂ alkyl, morepreferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferably C₂-C₁₂ alkenyl, morepreferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl (preferably C₂-C₁₂ alkynyl,more preferably C2-C6 alkynyl), C₅-C₂₄ aryl (preferably C₅-C₂₄ aryl),C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl). Within these substituent structures, the“alkyl,” “alkylene,” “alkenyl,” “alkenylene,” “alkynyl,” “alkynylene,”“alkoxy,” “aromatic,” “aryl,” “aryloxy,” “alkaryl,” and “aralkyl”moieties may be optionally fluorinated or perfluorinated. Additionally,reference to alcohols, aldehydes, amines, carboxylic acids, ketones, orother similarly reactive functional groups also includes their protectedanalogs. For example, reference to hydroxy or alcohol also includesthose substituents wherein the hydroxy is protected by acetyl (Ac),benzoyl (Bz), benzyl (Bn), β-Methoxyethoxymethyl ether (MEM),dimethoxytrityl, [bis-(4-methoxyphenyl)phenylmethyl] (DMT),methoxymethyl ether (MOM), methoxytrityl[(4-methoxyphenyl)diphenylmethyl, MMT), p-methoxybenzyl ether (PMB),methylthiomethyl ether, pivaloyl (Piv), tetrahydropyranyl (THP),tetrahydrofuran (THF), trityl (triphenylmethyl, Tr), silyl ether (mostpopular ones include trimethylsilyl (TMS), tert-butyldimethylsilyl(TBDMS), tri-iso-propylsilyloxymethyl (TOM), and triisopropylsilyl(TIPS) ethers), ethoxyethyl ethers (EE). Reference to amines alsoincludes those substituents wherein the amine is protected by a BOCglycine, carbobenzyloxy (Cbz), p-methoxybenzyl carbonyl (Moz or MeOZ),tert-butyloxycarbonyl (BOC), 9-fluorenylmethyloxycarbonyl (FMOC), acetyl(Ac), benzoyl (Bz), benzyl (Bn), carbamate, p-methoxybenzyl (PMB),3,4-dimethoxybenzyl (DMPM), p-methoxyphenyl (PMP), tosyl (Ts) group, orsulfonamide (Nosyl & Nps) group. Reference to substituent containing acarbonyl group also includes those substituents wherein the carbonyl isprotected by an acetal or ketal, acylal, or diathane group. Reference tosubstituent containing a carboxylic acid or carboxylate group alsoincludes those substituents wherein the carboxylic acid or carboxylategroup is protected by its methyl ester, benzyl ester, tert-butyl ester,an ester of 2,6-disubstituted phenol (e.g. 2,6-dimethylphenol,2,6-diisopropylphenol, 2,6-di-tert-butylphenol), a silyl ester, anorthoester, or an oxazoline. Preferred substituents are those identifiedherein as not or less affecting the silylation chemistries, for example,including those substituents comprising alkyls; alkoxides, aryloxides,aralkylalkoxides, protected carbonyl groups; aryls optionallysubstituted with F, Cl, —CF₃; epoxides; N-alkyl aziridines; cis- andtrans-olefins; acetylenes; pyridines, primary, secondary and tertiaryamines; phosphines; and hydroxides.

By “functionalized” as in “functionalized hydrocarbyl,” “functionalizedalkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and thelike, is meant that in the hydrocarbyl, alkyl, aryl, heteroaryl, olefin,cyclic olefin, or other moiety, at least one hydrogen atom bound to acarbon (or other) atom is replaced with one or more functional groupssuch as those described herein and above. The term “functional group” ismeant to include any of the substituents described herein with the ambitof “Fn.”.

In addition, the aforementioned functional groups may, if a particulargroup permits, be further substituted with one or more additionalfunctional groups or with one or more hydrocarbyl moieties such as thosespecifically enumerated above. Analogously, the above-mentionedhydrocarbyl moieties may be further substituted with one or morefunctional groups or additional hydrocarbyl moieties such as thosespecifically enumerated.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom ororganic moiety, and, thus, the description includes structures wherein anon-hydrogen substituent is present and structures wherein anon-hydrogen substituent is not present.

As used herein, the terms “organosilane” or “hydrosilane” may be usedinterchangeably and refer to a compound or reagent having at least onesilicon-hydrogen (Si—H) bond and preferably at least onecarbon-containing moiety. The organosilane may further contain asilicon-carbon, a silicon-oxygen (i.e., encompassing the term“organosiloxane”), a silicon-nitrogen bond, a silicon-silicon, or acombination thereof, and may be monomeric, dimeric (disilane) orcontained within an oligomeric or polymeric framework, including beingtethered to a heterogeneous or homogeneous support structure.

As used herein, the terms “hydrodisilane,” “organodisilane” and“disilane” are used interchangeably and refer to a compound or reagenthaving at least one Si—Si bond. These terms include those embodimentswhere the disilane contains at least one Si—H bond. The organodisilanemay further contain a silicon-carbon, a silicon-oxygen, asilicon-nitrogen bond, or a combination thereof, and may be monomeric,or contained within an oligomeric or polymeric framework, includingbeing tethered to a heterogeneous or homogeneous support structure.

As used herein, unless explicitly stated to the contrary, thehydrosilanes or hydrodisilanes are intended to refer to materials thatcontain no Si-halogen bonds. However, in some embodiments, thehydrosilanes or hydrodisilanes may contain a Si-halogen bond.

As used herein, the terms “dehydrogenative coupling,” “silylating” or“silylation” refer to the forming of silicon-oxygen bonds. As the namesuggests, dehydrogenative coupling may be seen as coupling of a O—H andSi—H bond to form a O—Si bond, with the release of H₂.

As used herein, the term “substantially free” or “substantially absenceof,” for example, of a transition-metal compound (or any of the othermaterials to which this term is applied), is intended to reflect thatthe system is effective for its intended purpose of dehydrogenativecoupling hydrosilanes and alcohols under the relatively mild conditionsdescribed herein, even in the absence of any exogenous (i.e.,deliberately added or otherwise) materials, in this casetransition-metal catalyst(s). While certain embodiments provide thattransition metals, including those capable of catalyzing silylationreactions, may be present within the systems or methods described hereinat levels normally associated with such catalytic activity (for example,in the case where the substrates comprise metallocenes), the presence ofsuch metals (either as catalysts or spectator compounds) is not requiredand in many cases is not desirable. As such, in many preferredembodiments, the system and methods are at least “substantially free,”if not completely free of transition-metal compounds (or the othermaterials to which this term is directed). Unless otherwise stated,then, the term “substantially free of a transition-metal compound” isdefined to reflect the absence of deliberately added materials(transition metals or the other materials to which this term isapplied). In other specified embodiment, the term “substantially free”refers to a condition in which the total level of transition metal (orthe other materials) in the reaction medium, independently or in thepresence of organic substrate, is less than about 5 ppm, as measured byICP-MS. When expressly stated as such, additional embodiments alsoprovide that the concentration of transition metals (or the othermaterials) is less than about 10 wt %, 5 wt %, 1 wt %, 100 ppm, 50 ppm,30 ppm, 25 ppm, 20 ppm, 15 ppm, 10 ppm, or 5 ppm to about 1 ppm or 0ppm. As used herein, the term “transition metal” is defined to included-block elements, for example Ag, Au, Co, Cr, Rh, Ir, Fe, Ru, Os, Ni,Pd, Pt, Cu, Zn, or combinations thereof. In further specific independentembodiments, the concentration of Ni, as measured by ICP-MS, is lessthan 25 ppm, less than 10 ppm, less than 5 ppm, or less than 1 ppm. Theterm “substantially free” is applied in this context to superbases,fluoride ions, and crown ethers. As used herein, the terms “crown ether”is intended to encompass “cryptands” and other cyclic or caged materialcontaining several ether groups capable of binding sodium and especiallypotassium cations, for example 12-crown-4, 15-crown-5, 18-crown-6,dibenzo-18-crown-6, diaza-18-crown-6, and 2.2.2-cryptand materials. Inpreferred embodiments, the presence of these types of chelants, or othersimilar Na⁺ or K⁺ selective binding agents are absent

While it may not be necessary to limit the system's exposure to waterand oxygen, in some embodiments, the chemical systems and the methodsare done in an environment substantially free of water, oxygen, or bothwater and oxygen. In other embodiments, air and/or water are present.Unless otherwise specified, the term “substantially free of water”refers to levels of water less than about 500 ppm and “substantiallyfree of oxygen” refers to oxygen levels corresponding to partialpressures less than 1 torr. Where stated, additional independentembodiments may provide that “substantially free of water” refers tolevels of water less than 1.5 wt %, 1 wt %, 0.5 wt %, 1000 ppm, 500 ppm,250 ppm, 100 ppm, 50 ppm, 10 ppm, or 1 ppm and “substantially free ofoxygen” refers to oxygen levels corresponding to partial pressures lessthan 50 torr, 10 torr, 5 torr, 1 torr, 500 millitorr, 250 millitorr, 100millitorr, 50 millitorr, or 10 millitorr. In the General Proceduredescribed herein, deliberate efforts were made to exclude both water andoxygen, unless otherwise specified.

The term “silyl ether” refers to product of the reactions as describedherein, comprising at least one C—O—Si linkage, as would be understoodby those skilled in the art.

The following listing of embodiments is intended to complement, ratherthan displace or supersede, the previous descriptions.

Embodiment 1

A method comprising contacting substrate (preferably an organicsubstrate) having at least one hydroxy (e.g., organic alcohol) moietywith a mixture of at least one hydrosilane and a sodium and/or potassiumhydroxide, the contacting resulting in the formation of adehydrogenatively coupled silyl ether. In related Aspects of thisEmbodiment, the substrate is or comprises an inorganic substrate, suchas a hydrated oxide (e.g., of alumina, silica, titania, or zirconia) orwater. In the former case, the product is a silylated inorganic surface;in the latter case, the product is a siloxane, for example, a mono-,di-, or polysilane and/or a cyclic polysiloxane. In certain Aspects ofthis Embodiment, the method is conducted in the complete or substantialabsence of transition metal ions, compounds, or catalysts. In otherAspects of this Embodiment, the methods are conducted in the substantialabsence of “superbases,” such as alkoxides, hydrides, alkyl lithium,anionic amides, or phosphines reagents, or any chemical known to enhancethe activity of the NaOH or KOH (e.g., crown ethers or cryptands). Inother Aspects of this Embodiment, the methods are conducted in thecomplete or substantial absence of fluoride ion (typically present astetraalkyl ammonium fluoride, for example). In still other Aspects ofthis Embodiment, the methods are conducted using aprotic polar solventssuch as acetonitrile, dimethylacetamide, dimethyl formamide,dimethylsulfoxide, glycols or polyglycols (including, for example,dimethoxyethane, DME), optionally substituted dioxanes, dialkyl ethers(e.g., diethyl, dimethyl ether), hexamethylphosphoramide (HMPA),optionally substituted THF and furans, and N-methylpyrrolidone (NMP).Oxygen donor solvents, such as THF, optionally in the presence of DMF,have been shown to work well in these reactions.

Embodiment 2

The method of Embodiment 1, wherein the hydrosilane contains at leastone Si—H bond and preferably has a structure of Formula (I) or ofFormula (II):

(R)_(3-m)Si(H)_(m+1)  (I)

(R)_(2-m)(H)_(m+1)Si—Si(R)_(3-m)(H)_(m)  (II)

where: m is independently 0, 1, or 2; and each R is independentlyoptionally substituted C₁₋₂₄ alkyl or heteroalkyl, optionallysubstituted C₂₋₂₄ alkenyl or heteroalkenyl, optionally substituted C₂₋₂₄alkynyl or heteroalkynyl, optionally substituted 6 to 18 ring memberedaryl or 5 to 18 ring membered heteroaryl, optionally substituted 6 to 18ring-membered alkaryl or 5 to 18 ring-membered heteroalkaryl, optionallysubstituted 6 to 18 ring-membered aralkyl or 5 to 18 ring-memberedheteroaralkyl, optionally substituted —O—C₁₋₂₄ alkyl or heteroalkyl,optionally substituted 6 to 18 ring-membered aryloxy or 5 to 18ring-membered heteroaryloxy, optionally substituted 6 to 18ring-membered alkaryloxy or 5 to 18 ring-membered heteroalkaryloxy, oroptionally substituted 6 to 18 ring-membered aralkoxy or 5 to 18ring-membered heteroaralkoxy, and, if substituted, the substituents maybe phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C₁-C₂₀alkylsulfanyl, C₅-C₂₀ arylsulfanyl, C₁-C₂₀ alkylsulfonyl, C₅-C₂₀arylsulfonyl, C₁-C₂₀ alkylsulfinyl, 5 to 12 ring-membered arylsulfinyl,sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C₁-C₂₀alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl,carboxyl, carboxylato, mercapto, formyl, C₁-C₂₀ thioester, cyano,cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy,styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, orhalogen, or a metal-containing or metalloid-containing group, where themetalloid is Sn or Ge, where the substituents may optionally provide atether to an insoluble or sparingly soluble support media comprisingalumina, silica, or carbon. In individual Aspects of this Embodiment, mis 0, m is 1, m is 2. The compounds of Formula (I) and Formula (II)represent independent Aspects of this Embodiment.

Embodiment 3

The method of Embodiment 1 or 2, wherein the hydrosilane is (R)₃SiH,(R)₂SiH₂, or (R)SiH₃, where R is independently C₁₋₆alkoxy, C₁₋₆alkyl,C₂₋₆alkenyl, C₆₋₂₄aryl, C₇₋₂₅aryloxy, a 5- or 6-ring memberedheteroaryl, aralkyl, or heteroaralkyl compound or moiety.

Embodiment 4

The method of any one of Embodiments 1 to 3, wherein the alkali metalhydroxide is sodium hydroxide (NaOH).

Embodiment 5

The method of any one of Embodiments 1 to 4, wherein the alkali metalhydroxide is potassium hydroxide (KOH). It should be appreciated that inthese Embodiments, the KOH is present and used in the absence of crownether or other hydroxide activating chemistries.

Embodiment 6

The method of any one of Embodiments 2 to 5, wherein the hydrosilane isa hydrosilane of Formula (I), where m is 1.

Embodiment 7

The method of any one of Embodiments 2 to 5, wherein the hydrosilane isa hydrosilane of Formula (I), where m is 2.

Embodiment 8

The method of any one of Embodiments 1 to 7, wherein the hydrosilane isEtMe₂SiH, Et₃SiH, (n-Bu)₃SiH, (i-Pr)₃SiH, Et₂SiH₂, Ph₂MeSiH,(t-Bu)Me₂SiH, (t-Bu)₂SiH₂, PhMeSiH₂, PhMe₂SiH, BnMe₂SiH, (EtO)₃SiH,Me₂(pyridinyl)SiH, (i-Pr)₂(pyridinyl)SiH, or Me₃Si—SiMe₂H.

Embodiment 9

The method of any one of Embodiments 1 to 8, wherein the organicsubstrate having at least one organic alcohol moiety has a structure ofFormula (IIIA):

R¹—OH  (IIIA),

where R¹ comprises an optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₂₋₂₄ alkenyl, optionally substituted C₂₋₂₄ alkynyl,optionally substituted C₆₋₂₄ aryl, optionally substituted C₁₋₂₄heteroalkyl, optionally substituted 5- or 6-ring membered heteroaryl,optionally substituted C₇₋₂₄ aralkyl, optionally substitutedheteroaralkyl, or optionally substituted metallocene.

Embodiment 10

The method of any one of Embodiments 1 to 8, wherein the organicsubstrate having at least one organic alcohol moiety has structure ofFormula (IIIB):

HO—R²—OH  (IIIB),

where R² comprises an optionally substituted C₂₋₁₂ alkylene, optionallysubstituted C₂₋₁₂ alkenylene, optionally substituted C₆₋₂₄ arylene,optionally substituted C₁₋₁₂ heteroalkylene, or an optionallysubstituted 5- or 6-ring membered heteroarylene. In certain Aspects ofthis Embodiment, the organic substrate having at least one organicalcohol moiety is a catechol, a neopentyl-diol, or a pinacol.

Embodiment 11

The method of any one of Embodiments 1 to 8 or 10, wherein the organicsubstrate having at least one organic alcohol moiety is or comprises anoptionally substituted catechol compound or moiety or has a Formula(IV):

wherein n is from 0 to 6;

R^(M) and R^(N) are independently H or methyl

R^(D), R^(E), R^(F), and R^(G) are independently H, C₁₋₆ alkyl,optionally substituted phenyl, optionally substituted benzyl, optionallysubstituted 5- or 6-ring membered heteroaryl, wherein the optionalsubstituents are C₁₋₃ alkyl, C₁₋₃ alkoxy, or halo. In certain Aspects ofthis Embodiment, the organic substrate include substituted 1,2-diols,1,3-diols, 1,4-diols, these being substituted with one or more alkyl(including methyl) and/or aryl (including optionally substituted aryl orheteroaryl—e.g., pinacol, 2,4-dimethyl-pentane-2,4-diol,3-phenyl-butane-1,3-diol, or 2,2-dimethyl-propane-1,3-diol.

Embodiment 12

The method of any one of Embodiments 1 to 11, wherein the organicsubstrate having at least one organic alcohol moiety is polymeric.

Embodiment 13

The method of any one of Embodiments 1 to 12, wherein the at least oneorganic alcohol moiety comprises an aliphatic alcohol moiety.

Embodiment 14

The method of any one of Embodiments 1 to 13, wherein the at least oneorganic alcohol moiety comprises an aromatic or α-methyl aromaticalcohol moiety.

Embodiment 15

The method of any one of Embodiments 1 to 14, wherein the at least oneorganic alcohol moiety comprises an optionally substituted benzylicalcohol moiety.

Embodiment 16

The method of Embodiment 14, wherein at least one organic alcohol moietyis an optionally substituted phenol (or other aromatic alcohol moiety)and the at least one hydrosilane is (tert-butyl)₂Si(H)₂ (or a similarlybulky dihydrosilane), the reaction product comprising a di-tert-butylsilyl phenyl ether (or corresponding aromatic silyl ether). In relatedAspects of this Embodiment, any hydroxylated naphthalene or 5- or6-membered heteroaryl moiety made stand in place of the phenol. Withoutintending to limit the definition of the substitution on the phenol, incertain Aspects of this Embodiment, the phenol has a structure ofFormula (V), where n is 0, 1, 2, 3, 5, or 5, and R^(A) is optionally atleast one of aldehyde (CHO), C₁₋₆ alkyl, C₁₋₆ alkylcarbonyl(—C(O)—C₁₋₆alkyl), C₁₋₆ alkoxy, C₁₋₆ alkoxycarbonyl (—C(O)—C₁₋₆alkyl),—C(O)—C₆₋₂₄ aryl), —C(O)-5- or 6 membered heteroaryl, halo, nitrile, ornitro. In other Aspects of this Embodiment, n is 2, and two R^(A)'stogether with the phenyl ring form a fused 5- or 6 membered carbocyclicring or 5- or 6 membered mono- or diether ring. Such a reactions may berepresented schematically as:

It should be appreciated that an optionally substituted naphthol orhydroxylated 5- or 6-membered heteroaryl may stand in the place of thephenol, in which case the descriptions of this and the followingEmbodiments also include those Aspects where the structures are definedby the corresponding hydroxylated aromatic structures and are expectedto be operable as described for the phenol derivative.

Embodiment 17

The method of Embodiment 16, further comprising converting thedi-tert-butyl silyl phenyl ether to a di-tert-butyl hydroxy silyl phenylether. Again, other aromatic silyl ethers are considered within thescope of this Embodiment. In certain Aspects of this Embodiment, thisstep further comprises contacting the di-tert-butyl silyl phenyl etherdescribed in Embodiment 16 with a base to form a di-tert-butyl hydroxysilyl phenyl ether. Without intending to limit the definition of thesubstitution of the substrates, in certain Aspects of this Embodiment,the di-tert-butyl silyl phenyl ether has a structure of Formula (VI),where n is 0, 1, 2, 3, 5, or 5, and R^(A) are described as in Embodiment16 and the di-tert-butyl hydroxy silyl phenyl ether of Formula (VII) iscorrespondingly substituted. In certain Aspects of this of thisEmbodiment, the base comprises a form of hydroxide, such as aqueouscarbonate or basic (hydroxide-containing) DMF, as described for examplein Huang, J. Am. Chem. Soc., 2011, 133 (44), 17630-17633. Such areaction may be represented schematically as:

and together Embodiments 16 and 17 may be represented by the schematic:

Embodiment 18

The method of Embodiment 17, further comprising converting thedi-tert-butyl hydroxy silyl phenyl ether to a catechol. Again, otheraromatic hydroxy silyl ethers are considered within the scope of thisEmbodiment. In certain Aspects of this Embodiment, this step furthercomprises contacting the di-tert-butyl hydroxy silyl phenyl ether ofEmbodiment 17 with an acetoxylating reagent in the presence of apalladium catalyst to form to a catechol. Again, without intending tolimit the definition of the substitution of the substrates, in certainAspects of this Embodiment, the di-tert-butyl hydroxy silyl phenyl etherdescribed in Embodiment 17 has a structure of Formula (VII), where n is0, 1, 2, 3, 5, or 5, and R^(A) are described as in Embodiment 16, andthe corresponding catechol of Formula (IX) is correspondinglysubstituted. In certain Aspects of this of this Embodiment, theacetoxylating reagent is or comprises PhI(OAc)₂, as described in Huang,J. Am. Chem. Soc., 2011, 133 (44), 17630-17633, which describes thistransformation as a highly site-selective silanol-directed, Pd-catalyzedC—H oxygenation of phenols into catechols that operates via asilanol-directed acetoxylation, followed by a subsequent acid-catalyzedcyclization reaction into a cyclic silicon-protected catechol. Thedesilylation of the silacyle with TBAF to uncover the catechol productis described as routine. Exemplary reaction conditions in this referenceincludes reacting the 3-methyl derivative of the compound of Formula(VII) with Pd(OPiv)₂ (5 mol %), PhI(OAc)₂ (2 eq) in toluene at 100° C.,for 6-12 hrs., followed by reaction with TBAF in THF. Such a reactionmay be represented schematically as:

Embodiment 19

The method of Embodiment 17, further comprising converting thedi-tert-butyl hydroxy silyl phenyl ether to an ortho-alkenylated phenol.Again, other aromatic hydroxy silyl ethers are considered within thescope of this Embodiment. In certain Aspects of this Embodiment, thisstep further comprises contacting the di-tert-butyl hydroxy silyl phenylether of Embodiment 17 with a terminal olefin in the presence of apalladium catalyst to form an ortho-alkenylated phenol. Again, withoutintending to limit the definition of the substitution of the substrates,in certain Aspects of this Embodiment the terminal olefin has astructure comprising Formula (X):

where R^(B) is H or C₁₋₁₂ alkyl and R^(C) is aldehyde, —C(O)—C₁₋₁₂alkyl, —C(O)—OC₁₋₁₂ alkyl, —S(O)₂—C₁₋₁₂ alkyl, —S(O)₂—C₆₋₂₄ aryl,—S(O)₂—OC₁₋₁₂ alkyl, —S(O)₂—OC₆₋₂₄ aryl, optionally substituted (withone or more halo or C₁₋₆ alkyl) phenyl, or an optionally substituted 5-or 6-membered heterocyclic group. In certain independent Aspects of thisEmbodiment, the di-tert-butyl hydroxy silyl phenyl ether described inEmbodiment 17 has a structure of Formula (VII), the ortho-alkenylatedphenol has a structure of Formula (XI), where n is 0, 1, 2, 3, 5, or 5,and R^(A) are described as in Embodiment 16, and the correspondingortho-alkenylated phenol is correspondingly substituted. C. Huang, etal., J. Am. Chem. Soc., 2011, 133 (32), pp 12406-12409 describes thistransformation as silanol-directed, Pd(II)-catalyzed ortho-C—Halkenylation of phenols. Exemplary reaction conditions in this referenceincludes reacting the 3,4-dimethyl derivative of the compound of Formula(VII) with a variety of functionalized terminal olefins (2-4 equiv) inthe presence of Pd(OAC)₂ (10 mol %), (+)menthyl(O₂C)-Leu-OH (20 mol %)),Li₂CO₃ (1 equiv), and AgOAc (4 equiv), in C₆F₆ at 100° C., followed byroutine desilylation using TBAF/THF. Such a reaction may be representedschematically as:

Embodiment 20

The method of Embodiment 17, further comprising converting thedi-tert-butyl hydroxy silyl phenyl ether to an ortho-carboxylic acidphenol. Again, other aromatic analogs are considered within the scope ofthis Embodiment. In certain Aspects of this Embodiment, this stepfurther comprises contacting the di-tert-butyl hydroxy silyl phenylether of Embodiment 17 with carbon monoxide (CO) in the presence of apalladium catalyst to form an ortho-carboxylic acid phenol. Withoutintending to limit the definition of the substitution of the substrates,in certain Aspects of this Embodiment, the di-tert-butyl hydroxy silylphenyl ether described in Embodiment 17 has a structure of Formula(VII), where n is 0, 1, 2, 3, 5, or 5, and RA are described as inEmbodiment 16, and the corresponding ortho-carboxylic acid phenol ofFormula (XIII) is correspondingly substituted. This transformation isdescribed in Y. Wang, et al., Angew Chem Int Ed Engl. 2015 Feb. 9;54(7): 2255-2259. Exemplary reaction conditions in this referenceincludes reacting the 3-tert-butyl derivative of the compound of Formula(VII) with CO in the presence of Pd(OAC)₂ (10 mol %), Boc-Leu-OH (20 mol%)), AgOAc (3 equiv), and CF₃CH₂OH (3 equiv) in dichloroethane at 95° C.for 18 hours, to form the cyclic derivative corresponding to Formula(XII), followed by routine desilylation using TBAF/THF to form thesalicyclic derivative (Formula (XIII)). Such a reaction may berepresented schematically as:

Embodiment 21

The method of any one of Embodiments 1 to 15, wherein the at least onehydrosilane is (R^(J))(R^(K))Si(H)₂, where R^(J) comprises an optionallysubstituted phenyl, optionally substituted naphthyl, or optionallysubstituted 5- or 6-membered heteroaryl moiety and where R^(K) is a C₁₋₃alkyl.

Embodiment 22

The method of Embodiment 21, wherein R^(K) is methyl and the organicsubstrate having at least one organic alcohol moiety is

the product of the reaction comprising a cyclic dioxasilolane. Incertain Aspects of this Embodiment, the product cyclic dioxasilolane hasa structure of Formula (XV);

wherein n is from 0 to 6; and

R^(D), R^(E), R^(F), and R^(G) are defined as above in Embodiment 11 asindependently H, C₁₋₆ alkyl, optionally substituted phenyl, optionallysubstituted benzyl, optionally substituted 5- or 6-ring memberedheteroaryl, wherein the optional substituents are C₁₋₃ alkyl, C₁₋₃alkoxy, or halo. Again, other substituted aromatic analogs areconsidered within the scope of this Embodiment. In some Aspects, thereaction may be represented schematically as:

Embodiment 23

The method of Embodiment 21 or 22, wherein R^(J) comprises an optionallysubstituted phenyl and the organic substrate having at least one organicalcohol moiety is 3-phenyl-butane-1,3-diol,2,2-dimethyl-propane-1,3-diol, catechol, or pinacol. Without intendingto necessarily limit the substituent pattern on the optionallysubstituted phenyl, in some Aspects of this Embodiment, the structuresof Formula (XIV) may be characterized as having the structure of Formula(XIV-A) and the product of the method having a structure of any one ofFormulae (XV-A), (XV-A1), (XV-A2), or (XV-A3). In some Aspects of thisEmbodiment, (R^(A))_(n) may be defined as described elsewhere herein(for example, in Embodiment 11).

Embodiment 24

The method of any one of Embodiments 21 to 23, further comprisingreacting the compound of Formula (XV) with an aromatic bromide or iodidein the presence of a palladium catalyst under conditions sufficient tocouple the aromatic R^(J) moiety to the aromatic bromide or iodide toform a biaromatic product. Exemplary conditions are described elsewhereherein.

Embodiment 25

The method of any one of Embodiments 21 to 23, further comprisingreacting the compound of Formula (XV) with C₁₋₆ acrylate ester in thepresence of a rhodium catalyst under conditions sufficient to couple thearomatic R^(J) moiety with the C₁₋₆ acrylate ester to form abeta-aromatic substituted C₁₋₆ propionate ester product. Exemplaryconditions are described elsewhere herein.

Embodiment 26

The method of any one of claims 21 to 23, further comprising reactingthe compound of Formula (XV) with an optionally substitutedbenzimidazole in the presence of a copper catalyst under conditionssufficient to aminate the benzimidazole with the aromatic R^(J) moiety.Exemplary conditions are described elsewhere herein.

Embodiment 27

A composition comprising or consisting essentially of (a) at least onehydrosilane; (b) sodium and/or potassium hydroxide; (c) an organicsubstrate having at least one organic alcohol moiety; and optionally (d)a silyl ether resulting from the dehydrogenative coupling of the atleast one hydrosilane and the at least one alcohol moiety. As describedin Embodiment 1, certain independent Aspects of this Embodiment 27provide that the composition is substantially free of absence oftransition metal catalysts; substantially free of “superbases,” such asalkoxides, hydrides, alkyl lithium reagents, or any chemical known toenhance the activity of the NaOH or KOH (e.g., crown ethers), and/orsubstantially free of added fluoride ion. In still other Aspects of thisEmbodiment, the compositions comprise aprotic polar solvents such asacetonitrile, dimethylacetamide, dimethyl formamide, dimethylsulfoxide,polyglycols (including, for example, dimethoxyethane, DME), optionallysubstituted dioxanes, dialkyl ethers (e.g., diethyl, dimethyl ether),hexamethylphosphoramide (HMPA), optionally substituted THF and furans,and N-methylpyrrolidone (NMP). The presence of NaOH, KOH, or acombination of NaOH and KOH represent independent Aspects of thisEmbodiment.

Embodiment 28

The composition of Embodiment 27, wherein the hydrosilane has astructure of Formula (I) or a hydrodisilane structure of Formula (II):

(R)_(3-m)Si(H)_(m+1)  (I)

(R)_(2-m)(H)_(m+1)Si—Si(R)_(3-m)(H)_(m)  (II)

where: m is independently 0, 1, or 2; and each R is independentlyoptionally substituted C₁₋₂₄ alkyl or heteroalkyl, optionallysubstituted C₂₋₂₄ alkenyl or heteroalkenyl, optionally substituted C₂₋₂₄alkynyl or heteroalkynyl, optionally substituted 6 to 18 ring memberedaryl or 5 to 18 ring membered heteroaryl, optionally substituted 6 to 18ring-membered alkaryl or 5 to 18 ring-membered heteroalkaryl, optionallysubstituted 6 to 18 ring-membered aralkyl or 5 to 18 ring-memberedheteroaralkyl, optionally substituted —O—C₁₋₂₄ alkyl or heteroalkyl,optionally substituted 6 to 18 ring-membered aryloxy or 5 to 18ring-membered heteroaryloxy, optionally substituted 6 to 18ring-membered alkaryloxy or 5 to 18 ring-membered heteroalkaryloxy, oroptionally substituted 6 to 18 ring-membered aralkoxy or 5 to 18ring-membered heteroaralkoxy, and, if substituted, the substituents maybe phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C₁-C₂₀alkylsulfanyl, C₅-C₂₀ arylsulfanyl, C₁-C₂₀ alkylsulfonyl, C₅-C₂₀arylsulfonyl, C₁-C₂₀ alkylsulfinyl, 5 to 12 ring-membered arylsulfinyl,sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C₁-C₂₀alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl,carboxyl, carboxylato, mercapto, formyl, C₁-C₂₀ thioester, cyano,cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy,styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, orhalogen, or a metal-containing or metalloid-containing group, where themetalloid is Sn or Ge, where the substituents may optionally provide atether to an insoluble or sparingly soluble support media comprisingalumina, silica, or carbon. In individual Aspects of this Embodiment, mis 0, m is 1, m is 2. In certain independent Aspects of this embodiment,the hydrosilane is a compound of Formula (I); in other Aspects, thehydrosilane is a compound of Formula (II). In other independent Aspectsof this Embodiment, the hydrosilane is a hydrosilane of Formula (I),where m is 1 or where m is 2. In still other Aspects, the hydrosilane isor comprises EtMe₂SiH, Et₃SiH, (n-Bu)₃SiH, (i-Pr)₃SiH, Et₂SiH₂,Ph₂MeSiH, (t-Bu)Me₂SiH, (t-Bu)₂SiH₂, PhMeSiH₂, PhMe₂SiH, BnMe₂SiH,(EtO)₃SiH, Me₂(pyridinyl)SiH, (i-Pr)₂(pyridinyl)SiH, or Me₃Si—SiMe₂H

Embodiment 29

The composition of Embodiments 27 or 28, wherein the organic substratehaving at least one organic alcohol moiety has a formula of R¹—OH orHO—R²—OH, as describe elsewhere herein. In some Aspects of thisEmbodiment, the organic substrate having at least one organic alcoholmoiety is or comprises an optionally substituted catechol compound ormoiety or has a Formula (IV), or its various permutations as describedabove:

In independent Aspects of this Embodiment, the organic substrate may bepolymeric, comprise an aliphatic alcohol moiety, comprise an aromatic orα-methyl aromatic alcohol moiety, or comprises an optionally substitutedbenzylic alcohol moiety.

Embodiment 30

The composition of any one of Embodiments 27 to 29, wherein thehydrosilane is (tert-butyl)₂Si(H)₂, at least one organic alcohol moietyis an optionally substituted phenol, naphthol, or hydroxylated 5- or6-membered heteroaryl, and the reaction product comprises thecorresponding di-tert-butyl silyl ether.

It should be appreciated that an optionally substituted naphthol orhydroxylated 1 may stand in the place of the phenol, in which case thedescriptions of this and the following Embodiments also include thoseAspects where the structures are defined by the correspondinghydroxylated aromatic structures and are expected to be operable asdescribed for the phenol derivative.

Embodiment 31

The composition of any one of Embodiments 27 to 29, wherein the at leastone hydrosilane is (R^(J))(R^(K))Si(H)₂, where R^(J) comprises anoptionally substituted phenyl, optionally substituted naphthyl, oroptionally substituted 5- or 6-membered heteroaryl as describedelsewhere herein and where R^(K) is a C₁₋₃ alkyl. Again, othersubstituted aromatic analogs are considered within the scope of thisEmbodiment.

Embodiment 32

The composition of Embodiment 31, wherein R^(K) is methyl and theorganic substrate having at least one organic alcohol moiety is orcomprises a compound of Formula (IV) or any of the permutations of thisstructure described elsewhere herein:

In certain Aspects of this Embodiment, the reaction product is presentand comprises as cyclic dioxasilolane. In certain Aspects of thisEmbodiment, the product cyclic dioxasilolane has a structure of Formula(XV), or any of the permutations of this structure described elsewhereherein, including but not limited to structures of Formulae (XV-A),(XV-A1), (XV-A2), or (XV-A3).

EXAMPLES

The following Examples are provided to illustrate some of the conceptsdescribed within this disclosure. While each Example is considered toprovide specific individual embodiments of composition, methods ofpreparation and use, none of the Examples should be considered to limitthe more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees C., pressure is at ornear atmospheric.

Example 1. Materials and Methods

Unless otherwise stated, reactions were performed in oven-driedbrand-new Fisherbrand scintillation vials flushed with argon or inflame-dried Schlenk flasks under argon connected on a Schlenk line usingdry, degassed solvents and brand-new stirring bars. Solvents were driedby passage through an activated alumina column under argon. Reactionprogress was monitored by thin-layer chromatography (TLC) or GC-FIDanalyses. TLC was performed using E. Merck silica gel 60 F254 precoatedglass plates (0.25 mm) and visualized by UV fluorescence quenching,phosphomolybdic acid, or KMnO₄ staining. Silicycle SiliaFlash P60Academic Silica gel (particle size 40-63 nm) was used for flashchromatography. ¹H NMR spectra were recorded on a Varian Inova 500 MHzspectrometer in CDCl₃, THF-d8, or C₆D₆ and are reported relative toresidual solvent peak at δ 7.26 ppm, δ 3.58 ppm, or δ 7.16 ppmrespectively. ¹³C NMR spectra were recorded on a Varian Inova 500 MHzspectrometer (126 MHz) in CDCl₃, THF-d8, or C₆D₆ and are reportedrelative to residual solvent peak at δ 77.16 ppm, δ 67.21 ppm, or δ67.21 ppm respectively. Data for ¹H NMR are reported as follows:chemical shift (δ ppm) (multiplicity, coupling constant (Hz),integration). Multiplicities are reported as follows: s=singlet,d=doublet, t=triplet, q=quartet, p=pentet, sept=septet, m=multiplet, brs=broad singlet, br d=broad doublet, app=apparent. Data for ¹³C NMR arereported in terms of chemical shifts (δ ppm). IR spectra were obtainedon a Perkin Elmer Spectrum BXII spectrometer using thin films depositedon NaCl plates and reported in frequency of absorption (cm⁻¹). GC-FIDanalyses were obtained on an Agilent 6890N gas chromatograph equippedwith a HP-5 (5%-phenyl)-methylpolysiloxane capillary column (Agilent).GC-MS analyses were obtained on an Agilent 6850 gas chromatographequipped with a HP-5 (5%-phenyl)-methylpolysiloxane capillary column(Agilent). High resolution mass spectra (HRMS) were acquired from theCalifornia Institute of Technology Mass Spectrometry Facility. ICP-MSanalysis was conducted at the California Institute of Technology MassSpectrometry Facility.

Silanes were purchased from Aldrich and distilled before use. NaOH waspurchased from Aldrich (semiconductor grade, pellets, 99.99% tracemetals basis) and was pulverized (mortar and pestle) and heated (150°C.) under vacuum prior to use. Powdered and vacuum-dried (as above) ACSgrade ≥97% NaOH from Aldrich gives identical results. Alcohol and phenolsubstrates were purchased from Aldrich, TCI, or Acros.

Example 2. Screening Studies Example 2.1. Reaction Optimization

Procedure for Reaction Condition Optimization:

In a nitrogen-filled glovebox, catalyst and alcohol Ta (0.1 mmol, 1equiv) were added to a 2 dram scintillation vial equipped with amagnetic stirring bar. Next, hydrosilane and solvent (0.1 mL) wereadded. The vial was sealed and the mixture was stirred at the indicatedtemperature for the indicated time. The vial was then removed from theglovebox, diluted with diethyl ether (1 mL), and concentrated underreduced pressure. The yield was determined by ¹H NMR or GC analysis ofthe crude mixture using an internal standard.

The initial studies showed that THF and DME proved to be suitablesolvents. The addition of DMF to reaction mixtures enabled thesilylation in challenging cases; curiously, several substrates failed tosilylate without the addition of DMF. See characterization data (PartII) for a comprehensive view of all substrates that required addition ofDMF. No product was observed in the absence of the hydroxide catalyst.

Example 2.2. Experimental and Analytics Example 2.2.1. General Procedurefor Cross-Dehydrogenative O—H Silylation and Characterization Data

NaOH (0.05 mmol, 10 mol %) was added to a hot, oven-dried 2 dramscintillation vial equipped with a magnetic stirring bar, and the vialwas purged with argon until cool. Alcohol (0.5 mmol, 1 equiv) was thenadded under a steady stream of argon, followed by solvent (0.5 mL) andsilane (0.75 mmol, 1.5 equiv). The vial was then sealed and the mixturewas stirred at the indicated temperature for the indicated time. Afterthe reaction was complete, the reaction mixture was diluted with diethylether (2 mL), filtered through a short pad of silica gel, andconcentrated under reduced pressure. Volatiles were removed under highvacuum and the resultant material was purified by silica gel flashchromatography if necessary to give the desired O—Si product.

Example 2.2.2. (Benzyloxy)dimethyl(phenyl)silane 2a

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), benzyl alcohol (54 mg, 0.5 mmol, 1.0equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL oftetrahydrofuran (THF) at 25° C. for 18 h. The desired product 2a (113.9mg, 94% yield) was obtained as a colorless oil by silica gel flashchromatography (5% EtOAc in hexanes). R_(f)=0.53 (5% EtOAc in hexanes);¹H NMR (500 MHz, CDCl₃) δ 7.70-7.66 (m, 2H), 7.48-7.42 (m, 3H),7.40-7.35 (m, 4H), 7.30 (dddd, J=6.7, 6.2, 3.1, 1.7 Hz, 1H), 4.77 (s,2H), 0.49 (s, 6H). This compound has been previously characterized. SeeMitsudome, T., et al., Chemistry—A European Journal, 2013, 19 (43),14398-14402.

Example 2.2.3. (Benzyloxy)triethylsilane 2b

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), benzyl alcohol (54 mg, 0.5 mmol, 1.0equiv), Et₃SiH (87 mg, 120 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL oftetrahydrofuran (THF) at 45° C. for 18 h. The desired product 2b (101.2mg, 91% yield) was obtained as a colorless oil by silica gel flashchromatography (5% EtOAc in hexanes). R_(f)=0.27 (5% EtOAc in hexanes);¹H NMR (500 MHz, CDCl₃) δ 7.36-7.31 (m, 4H), 7.27-7.23 (m, 1H), 4.75 (s,2H), 1.00 (t, J=8.0 Hz, 9H), 0.67 (q, J=7.9 Hz, 5H). This compound hasbeen previously characterized. See Abri, A., et al., Journal of theChinese Chemical Society, 2012, 59 (11), 1449-1454.

Example 2.2.4. (Benzyloxy)(methyl)diphenylsilane 2c

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), benzyl alcohol (54 mg, 0.5 mmol, 1.0equiv), Ph₂MeSiH (149 mg, 150 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL oftetrahydrofuran (THF) at 25° C. for 18 h. The desired product 2c (129.4mg, 85% yield) was obtained as a colorless oil by silica gel flashchromatography (5% EtOAc in hexanes). R_(f)=0.50 (5% EtOAc in hexanes);¹H NMR (500 MHz, CDCl₃) δ 7.72 (p, J=7.7, 7.0 Hz, 3H), 7.69-7.58 (m,2H), 7.54-7.37 (m, 10H), 4.90 (dt, J=13.7, 3.0 Hz, 2H), 0.77 (dt,J=14.1, 2.9 Hz, 3H). This compound has been previously characterized.See Igarashi, M., et al. Chemistry Letters, 2014, 43 (4), 429-431

Example 2.2.5. (Benzyloxy)(tert-butyl)dimethylsilane 2d

The general procedure was followed. The reaction was performed with NaOH(4.0 mg, 0.1 mmol, 20 mol %), benzyl alcohol (54 mg, 0.5 mmol, 1.0equiv), (t-Bu)Me₂SiH (87 mg, 124 μL, 1.5 mmol, 3.0 equiv), 0.25 mLdimethylformamide (DMF) and 0.25 mL of tetrahydrofuran (THF) at 65° C.for 24 h. The desired product 2d (66.2 mg, 60% yield) was obtained as acolorless oil by silica gel flash chromatography (5% EtOAc in hexanes).R_(f)=0.42 (5% EtOAc in hexanes); ¹H NMR (500 MHz, CDCl₃) δ 7.35 (d,J=4.6 Hz, 4H), 7.28-7.24 (m, 1H), 4.78 (d, J=0.6 Hz, 2H), 0.98 (s, 9H),0.14 (s, 6H). This compound has been previously characterized. SeeYamamoto, K., et al., Bulletin of the Chemical Society of Japan, 1989,62 (6), 2111-2113.

Example 2.2.6. (Benzyloxy)di-tert-butylsilane 2e

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), benzyl alcohol (54 mg, 0.5 mmol, 1.0equiv), (t-Bu)₂SiH₂ (108 mg, 148 μL, 0.75 mmol, 1.5 equiv), and 0.5 mLof tetrahydrofuran (THF) at 25° C. for 18 h. The desired product 2e(120.2 mg, 96% yield) was obtained as a colorless oil after removal ofvolatiles under high vacuum (45 mtorr) for 2 hours. ¹H NMR (500 MHz,CDCl₃) δ 7.39-7.34 (m, 4H), 7.29-7.25 (m, 1H), 4.88 (d, J=0.7 Hz, 2H),4.12 (s, 1H), 1.05 (s, 18H). This compound has been previouslycharacterized. See Curran, D. P. et al., Journal of the ChemicalSociety, Perkin Transactions 1: Organic and Bio-Organic Chemistry(1972-1999), 1995, 24, 3049-3060

Example 2.2.7. (Benzyloxy)triisopropylsilane 2f

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), benzyl alcohol (54 mg, 0.5 mmol, 1.0equiv), (i-Pr)₃SiH (119 mg, 154 μL, 0.75 mmol, 1.5 equiv), 0.25 mLdimethylformamide (DMF), and 0.25 mL of tetrahydrofuran (THF) at 65° C.for 18 h. The desired product 2f (112.4 mg, 85% yield) was obtained as acolorless oil by silica gel flash chromatography (5% EtOAc in hexanes).R_(f)=0.52 (5% EtOAc in hexanes); ¹H NMR (500 MHz, CDCl₃) δ 1H NMR (500MHz, Chloroform-d) d 7.40-7.32 (m, 4H), 7.27-7.23 (m, 1H), 4.87 (d,J=1.5 Hz, 2H), 1.26-1.17 (m, 3H), 1.15-1.11 (m, 18H). This compound hasbeen previously characterized. See Khalafi-Nezhad, A., et al.,Tetrahedron, 2000, 56 (38), 7503-7506.

Example 2.2.8. 1-(Benzyloxy)-1,1,2,2,2-pentamethyldisilane 2g

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), benzyl alcohol (54 mg, 0.5 mmol, 1.0equiv), Me₅Si₂H (99 mg, 137 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL oftetrahydrofuran (THF) at 25° C. for 24 h. Concentration of the reactionmixture and purification of the resulting residue via Kugelrohrdistillation (120 mTorr, 60° C.) gave 79.9 mg (67% yield) of 2g as acolorless oil. ¹H NMR (500 MHz, THF-d8) δ 7.31-7.24 (m, 4H), 7.21-7.15(m, 1H), 4.68 (q, J=0.7 Hz, 2H), 0.23 (s, 6H), 0.10 (s, 9H); ¹³C NMR(126 MHz, THF-d8) δ 142.61, 128.96, 127.71, 127.01, 66.02, −0.52, −1.79.IR (Neat Film NaCl) 3363, 3088, 3065, 3030, 2952, 2893, 1595, 1495,1453, 1376, 1259, 1246, 1207, 1091, 1067, 1026, 835, 803, 766, 729, 695,655, 617 cm⁻¹; HRMS (EI+) calc'd for C₁₂H₂₃OSi₂ [M+H]: 239.1288, found239.1295.

Example 2.2.9. Bis(benzyloxy)diethylsilane 2h

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), benzyl alcohol (108 mg, 1.0 mmol, 1.0equiv), Et₂SiH₂ (49 mg, 71 μL, 0.55 mmol, 0.55 equiv), and 1.0 mL oftetrahydrofuran (THF) at 25° C. for 18 h. The desired product 2h (120.8mg, 80% yield) was obtained as a colorless oil by silica gel flashchromatography (5% EtOAc in hexanes). R_(f)=0.43 (5% EtOAc in hexanes);¹H NMR (500 MHz, CDCl₃) δ 7.35 (d, J=4.4 Hz, 8H), 7.31-7.26 (m, 2H),4.82 (s, 4H), 1.05 (t, J=7.9 Hz, 6H), 0.76 (q, J=8.0 Hz, 4H). Thiscompound has been previously characterized. See Chatterjee, B., et al.,Chemical Communications, 2014, 50 (7), 888-890

Example 2.2.10. Bis(benzyloxy)(methyl)(phenyl)silane 2i

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), benzyl alcohol (108 mg, 1.0 mmol, 1.0equiv), MePhSiH₂ (67 mg, 76 μL, 0.55 mmol, 0.55 equiv), and 1.0 mL oftetrahydrofuran (THF) at 25° C. for 18 h. The desired product 2i (158.8mg, 95% yield) was obtained as a colorless oil by silica gel flashchromatography (5% EtOAc in hexanes). R_(f)=0.44 (5% EtOAc in hexanes);¹H NMR (500 MHz, CDCl₃) δ 1H NMR (500 MHz, Chloroform-d) d 7.76 (dd,J=7.9, 1.5 Hz, 2H), 7.49-7.43 (m, 3H), 7.39-7.37 (m, 8H), 7.33-7.28 (m,2H), 4.91-4.82 (m, 4H), 0.50 (s, 3H). This compound has been previouslycharacterized. See Kita, Y., et al., Tetrahedron Letters, 1983, 24 (12),1273-1276.

Example 2.2.11. ((4-Fluorobenzyl)oxy)dimethyl(phenyl)silane 4a

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 4-fluorobenzyl alcohol (63 mg, 0.5 mmol,1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), 0.2 mLdimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 25° C.for 18 h. The desired product 4a (146.0 mg, 79% yield) was obtained as acolorless oil by silica gel flash chromatography (5% EtOAc in hexanes).R_(f)=0.48 (5% EtOAc in hexanes); ¹H NMR (500 MHz, CDCl₃) δ 7.65-7.59(m, 2H), 7.46-7.37 (m, 3H), 7.31-7.25 (m, 2H), 7.06-6.97 (m, 2H), 4.67(q, J=0.8 Hz, 2H), 0.45 (s, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 162.14 (d,J=244.4 Hz), 137.50, 136.53 (d, J=2.9 Hz), 133.64, 129.90, 128.37 (d,J=8.3 Hz), 128.06, 115.19 (d, J=21.1 Hz), 64.48, −1.60. IR (Neat FilmNaCl) 3440, 3070, 3050, 3022, 2958, 2866, 1605, 1509, 1463, 1427, 1417,1375, 1294, 1253, 1221, 1155, 1117, 1082, 1014, 826, 789, 741, 700, 645cm⁻¹; HRMS (EI+) calc'd for C₁₅H₁₆OSiF [(M+H)−H₂]: 259.0955, found259.0951.

Example 2.2.11. ((4-Bromobenzyl)oxy)dimethyl(phenyl)silane 4b

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 4-bromobenzyl alcohol (94 mg, 0.5 mmol,1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), 0.2 mLdimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 65° C.for 24 h. The desired product 4b (146.2 mg, 91% yield) was obtained as acolorless oil by silica gel flash chromatography (5% EtOAc in hexanes).R_(f)=0.48 (5% EtOAc in hexanes); ¹H NMR (500 MHz, CDCl₃) δ 7.61 (dd,J=7.7, 1.8 Hz, 2H), 7.47-7.34 (m, 5H), 7.19 (dt, J=8.7, 0.7 Hz, 2H),4.66 (d, J=0.8 Hz, 2H), 0.44 (s, 6H). This compound has been previouslycharacterized. See Kennedy-Smith, J. J., et al., J. Amer. Chem. Soc.,2003, 125 (14), 4056-4057.

Example 2.2.12. Dimethyl((4-nitrobenzyl)oxy)(phenyl)silane 4c

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 4-nitrobenzyl alcohol (77 mg, 0.5 mmol,1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), 0.2 mLdimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 65° C.for 18 h. The desired product 4c (102.2 mg, 71% yield) was obtained as acolorless oil by silica gel flash chromatography (5% EtOAc in hexanes).R_(f)=038 (5% EtOAc in hexanes); ¹H NMR (500 MHz, CDCl₃) δ 8.21-8.15 (m,2H), 7.60 (dd, J=7.8, 1.7 Hz, 2H), 7.47 (dt, J=8.8, 0.8 Hz, 2H),7.44-7.38 (m, 3H), 4.79 (t, J=0.8 Hz, 2H), 0.47 (s, 6H); ¹³C NMR (126MHz, CDCl₃) δ 148.51, 147.18, 136.92, 133.59, 130.13, 128.18, 126.77,123.68, 64.03, −1.73. IR (Neat Film NaCl) 3423, 2958, 1641, 1608, 1519,1527, 1253, 1117, 1094, 856, 830, 786, 735, 700 cm⁻¹; HRMS (EI+) calc'dfor C₁₅H₁₈SiO₃N [M+H]: 288.1056, found 288.1058.

Example 2.2.11. Methyl 4-(((dimethyl(phenyl)silyl)oxy)methyl)benzoate 4d

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), methyl 4-(hydroxymethyl)benzoate (83 mg,0.5 mmol, 1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv),0.2 mL dimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at65° C. for 24 h. The desired product 4d (100.6 mg, 67% yield) wasobtained as a colorless oil by silica gel flash chromatography (gradient15% EtOAc to 30% EtOAc in hexanes). R_(f)=0.62 (15% EtOAc in hexanes);¹H NMR (500 MHz, CDCl₃) δ 8.01 (d, J=8.3 Hz, 2H), 7.63-7.60 (m, 2H),7.45-7.36 (m, 5H), 4.76 (d, J=0.8 Hz, 2H), 3.92 (s, 3H), 0.46 (s, 6H).This compound has been previously characterized. See Fernandez, A. C.,et al., Chem. Comm., 2005, 2, 213-214

Example 2.2.12. 4-(Methoxycarbonyl)benzyl4-(((dimethyl(phenyl)silyl)oxy)methyl)benzoate 4d-SI

Also isolated from the column was 4d-SI (36.9 mg, 34% silylationyield/17% yield based on methyl 4-(hydroxymethyl)benzoate stoichiometry)as a colorless solid. R_(f)=0.43 (15% EtOAc in hexanes); ¹H NMR (500MHz, CDCl₃) δ 8.08-8.03 (m, 4H), 7.62-7.58 (m, 2H), 7.51 (dt, J=8.6, 0.7Hz, 2H), 7.43-7.37 (m, 5H), 5.42 (s, 2H), 4.76 (d, J=0.8 Hz, 2H), 3.93(s, 3H), 0.44 (s, 6H); ¹³C NMR (126 MHz, CDCl₃) δ 166.88, 166.31,146.62, 141.30, 137.26, 133.61, 130.02, 129.97, 129.90, 128.63, 128.09,127.72, 126.27, 65.94, 64.53, 52.32, −1.64.

Example 2.2.13. ((4-Methoxybenzyl)oxy)dimethyl(phenyl)silane 4e

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 4-methoxybenzyl alcohol (69 mg, 0.5 mmol,1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mLof tetrahydrofuran (THF) at 25° C. for 18 h. The desired product 4e(117.9 mg, 87% yield) was obtained as a colorless oil by silica gelflash chromatography (5% EtOAc in hexanes). R_(f)=0.29 (5% EtOAc inhexanes); ¹H NMR (500 MHz, CDCl₃) δ 7.62 (dd, J=7.5, 2.0 Hz, 2H),7.44-7.37 (m, 3H), 7.25-7.20 (m, 2H), 6.87 (d, J=8.6 Hz, 2H), 4.64 (d,J=0.6 Hz, 2H), 3.81 (s, 3H), 0.42 (s, 6H). This compound has beenpreviously characterized. See Bideau, F. L., et al., Chem. Comm.(Cambridge, United Kingdom), 2001, 15, 1408-1409

Example 2.2.14. 3-(((Dimethyl(phenyl)silyl)oxy)methyl)pyridinesilane 4f

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), pyridin-3-ylmethanol (55 mg, 0.5 mmol,1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mLof tetrahydrofuran (THF) at 25° C. for 18 h. The desired product 4f(118.1 mg, 97% yield) was obtained as a colorless oil by removal ofvolatiles at 80° C. at 60 mTorr. ¹H NMR (500 MHz, CDCl₃) δ 8.52 (dt,J=2.3, 0.8 Hz, 1H), 8.49 (dd, J=4.8, 1.6 Hz, 1H), 7.65 (dtd, J=7.8, 1.7,0.9 Hz, 1H), 7.61-7.57 (m, 2H), 7.43-7.37 (m, 3H), 7.26 (ddd, J=7.9,4.8, 0.9 Hz, 1H), 4.70 (dt, J=0.6 Hz, 2H), 0.44 (s, 6H). This compoundhas been previously characterized. See Goldberg, Y., et al., SyntheticCommunications, 1990, 20 (16), 2439-2446.

Example 2.2.15. Dimethyl(phenyl)(thiophen-2-ylmethoxy)silane 4g

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), thiophen-2-ylmethanol (57 mg, 0.5 mmol,1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mLof tetrahydrofuran (THF) at 25° C. for 18 h. The desired product 4g(119.2 mg, 96% yield) was obtained as a colorless oil by removal ofvolatiles at 80° C. at 60 mTorr. ¹H NMR (500 MHz, CDCl₃) δ 7.68-7.63 (m,2H), 7.47-7.43 (m, 3H), 7.26 (dd, J=5.0, 1.3 Hz, 1H), 6.97 (dd, J=5.0,3.4 Hz, 1H), 6.94-6.91 (m, 1H), 4.87 (d, J=0.8 Hz, 2H), 0.47 (s, 6H).This compound has been previously characterized. See Goldberg, Y., etal., Journal of Organometallic Chemistry, 1991, 410 (2), 127-133.

Example 2.2.16. (Furan-2-ylmethoxy)dimethyl(phenyl)silane 4h

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), furfuryl alcohol (49 mg, 0.5 mmol, 1.0equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL oftetrahydrofuran (THF) at 45° C. for 18 h. The desired product 4h (101.1mg, 87% yield) was obtained as a colorless oil by removal of volatilesat 80° C. at 60 mTorr. ¹H NMR (500 MHz, CDCl₃) δ 7.62 (ddd, J=7.5, 2.4,1.3 Hz, 2H), 7.46-7.33 (m, 4H), 6.32 (dt, J=3.4, 1.8 Hz, 1H), 6.21 (t,J=2.5 Hz, 1H), 4.62 (d, J=2.0 Hz, 2H), 0.39-0.35 (m, 6H). This compoundhas been previously characterized. See Goldberg, Y., et al., Journal ofOrganometallic Chemistry, 1991, 410 (2), 127-133.

Example 2.2.17. Dimethyl(phenyl)((2,4,6-trimethylbenzyl)oxy)silane 4i

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), mesitylmethanol (75 mg, 0.5 mmol, 1.0equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), 0.2 mLdimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 65° C.for 18 h. Concentration of the reaction mixture and purification of theresulting residue via Kugelrohr distillation (100 mTorr, 210° C.) gave118.7 mg (84% yield) of 4i as a colorless oil. (Note: the purifiedmaterial obtained by Kugelrohr distillation was accompanied by ca. 5%unidentified by-products; however, further purification bychromatography was precluded by the instability of 4i on SiO₂ as well asits decomposition under prolonged heating). ¹H NMR (500 MHz, THF-d8) δ7.59-7.55 (m, 2H), 7.36-7.30 (m, 3H), 6.79-6.73 (m, 2H), 4.66 (s, 2H),2.24 (t, J=0.6 Hz, 6H), 2.20 (s, 3H), 0.35 (s, 6H); ¹³C NMR (126 MHz,THF-d8) δ 139.02, 137.93, 137.61, 134.72, 134.46, 130.42, 129.65,128.68, 59.98, 21.23, 19.79, −1.48. IR (Neat Film NaCl) 3421, 3069,3048, 3008, 2957, 2918, 1614, 1583, 1427, 1373, 1253, 1147, 1118, 1046,848, 829, 784, 740, 699, 644 cm⁻¹; HRMS (EI+) calc'd for C₁₆H₁₆FSi[(M+H)−H₂]: 283.1518, found 283.1526.

Example 2.2.18.2-(2-((Dimethyl(phenyl)silyl)oxy)ethyl)isoindoline-1,3-dione 4j

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 2-(2-hydroxyethyl)isoindoline-1,3-dione(96 mg, 0.5 mmol, 1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5equiv), 0.2 mL dimethylformamide (DMF) and 0.3 mL of tetrahydrofuran(THF) at 65° C. for 24 h. The desired product 4j (101.6 mg, 62% yield)was obtained as a colorless oil by silica gel flash chromatography (20%EtOAc in hexanes). R_(f)=0.45 (20% EtOAc in hexanes); ¹H NMR (500 MHz,Benzene-d6) δ 7.52-7.50 (m, 1H), 7.50 (dd, J=2.4, 0.6 Hz, 1H), 7.43 (dd,J=5.4, 3.0 Hz, 2H), 7.16-7.15 (m, 1H), 7.15-7.14 (m, 1H), 7.14 (d, J=2.3Hz, 1H), 6.87 (ddd, J=5.5, 3.0, 0.5 Hz, 2H), 3.74-3.67 (m, 2H),3.68-3.62 (m, 2H), 0.26 (s, 6H); ¹³C NMR (126 MHz, Benzene-d₆) δ 167.96,137.77, 133.81, 133.39, 132.66, 129.84, 128.13, 122.95, 60.16, 40.23,−1.81. IR (Neat Film NaCl) 2956, 1773, 1713, 1615, 1467, 1427, 1392,1362, 1319, 1252, 1189, 1116, 1022, 929, 859, 829, 788, 718, 700 cm⁻¹;HRMS (EI+) calc'd for C₁₈H₂₀O₃SiN [M+H]: 326.1213, found 326.1223.

Example 2.2.19. Dimethyl(octyloxy)(phenyl)silane 4k

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 1-octanol (65 mg, 0.5 mmol, 1.0 equiv),PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL oftetrahydrofuran (THF) at 25° C. for 18 h. The desired product 4k (111.1mg, 84% yield) was obtained as a colorless oil by silica gel flashchromatography (100% hexanes). R_(f)=0.49 (100% hexanes); ¹H NMR (500MHz, CDCl₃) δ 7.64-7.58 (m, 2H), 7.41 (dd, J=5.0, 1.9 Hz, 3H), 3.62 (t,J=6.7 Hz, 2H), 1.60-1.51 (m, 2H), 1.32-1.24 (m, 10H), 0.97-0.85 (m, 3H),0.41 (s, 6H). This compound has been previously characterized. SeeItagaki, S., et al., Chemistry Letters, 2013, 42 (9), 980-982

Example 2.2.20. Dimethyl((3-methylcyclohex-2-en-1-yl)oxy)(phenyl)silane4l

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 3-methylcyclohex-2-en-1-ol (56 mg, 0.5mmol, 1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and0.5 mL of tetrahydrofuran (THF) at 45° C. for 48 h. The desired product41 (113.4 mg, 92% yield) was obtained as a colorless oil by silica gelflash chromatography (5% EtOAc in hexanes). R_(f)=0.43 (5% EtOAc inhexanes); ¹H NMR (500 MHz, CDCl₃) δ 7.64-7.56 (m, 2H), 7.38 (dd, J=5.0,1.9 Hz, 3H), 5.34 (dd, J=3.1, 1.6 Hz, 1H), 4.20 (dt, J=5.0, 1.6 Hz, 1H),1.99-1.69 (m, 4H), 1.64 (tt, J=1.6, 0.9 Hz, 3H), 1.55-1.42 (m, 2H), 0.40(d, J=1.1 Hz, 6H); ¹³C NMR (126 MHz, CDCl₃) δ 138.64, 137.78, 133.69,129.59, 127.89, 125.14, 67.41, 32.13, 30.08, 23.80, 19.83, −0.80, −0.91.IR (Neat Film NaCl) 3423, 3069, 2935, 2862, 1645, 1427, 1251, 1116,1074, 1024, 992, 894, 880, 828, 786, 738, 700 cm⁻¹; HRMS (EI+) calc'dfor C₁₅H₂₁OSi [(M+H)−H₂]: 245.1362, found 245.1368.

Example 2.2.21. Dimethyl(phenyl)((5-phenylpentyl)oxy)silane 4m

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 5-phenylpentan-1-ol (82 mg, 0.5 mmol, 1.0equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL oftetrahydrofuran (THF) at 45° C. for 18 h. The desired product 4m (146.3mg, 98% yield) was obtained as a colorless oil by silica gel flashchromatography (5% EtOAc in hexanes). R_(f)=0.46 (5% EtOAc in hexanes);¹H NMR (500 MHz, CDCl₃) δ 7.63 (ddq, J=6.2, 1.9, 0.9 Hz, 2H), 7.46-7.41(m, 3H), 7.32 (tt, J=7.5, 0.9 Hz, 2H), 7.22 (ddt, J=9.9, 7.3, 1.3 Hz,3H), 3.65 (td, J=6.7, 1.1 Hz, 2H), 2.67-2.63 (m, 2H), 1.74-1.58 (m, 4H),1.47-1.38 (m, 2H), 0.44 (t, J=1.0 Hz, 6H); ¹³C NMR (126 MHz, CDCl₃) δ142.79, 138.10, 133.58, 129.66, 128.51, 128.34, 127.93, 125.71, 63.15,36.04, 32.57, 31.41, 25.59, −1.65. IR (Neat Film NaCl) 3385, 3067, 3025,2933, 2857, 1603, 1495, 1452, 1427, 1341, 1254, 1119, 1055, 831, 791,726, 698 cm⁻¹; HRMS (EI+) calc'd for C₁₉H₂₇OSi [M+H]: 299.1831, found299.1840.

Example 2.2.22. (Hex-2-yn-1-yloxy)dimethyl(phenyl)silane 4n

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), hex-2-yn-1-ol (49 mg, 0.5 mmol, 1.0equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL of 1tetrahydrofuran (THF) at 45° C. for 18 h. The desired product 4n (99.9mg, 86% yield) was obtained as a colorless oil by silica gel flashchromatography (5% EtOAc in hexanes). R_(f)=0.43 (5% EtOAc in hexanes);¹H NMR (500 MHz, CDCl₃) δ 77.62-7.59 (m, 2H), 7.42-7.36 (m, 3H), 4.27(t, J=2.2 Hz, 2H), 2.16 (tt, J=7.1, 2.2 Hz, 2H), 1.51 (h, J=7.3 Hz, 2H),0.97 (t, J=7.3 Hz, 3H), 0.45 (s, 6H); ¹³C NMR (126 MHz, CDCl₃) δ 137.36,133.71, 129.84, 127.97, 85.99, 78.37, 51.93, 22.11, 20.92, 13.66, −1.46.Note: this product decomposes slowly in CDCl₃. IR (Neat Film NaCl) 3420,2956, 1646, 1254, 1118, 1067, 1026, 830, 789, 726, 698 cm⁻¹; HRMS (EI+)calc'd for C₁₄H₁₉OSi [M+H]: 231.1205, found 231.1207.

Example 2.2.23. (Cyclopropylmethoxy)dimethyl(phenyl)silane 4o

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), cyclopropanemethanol (36 mg, 0.5 mmol,1.0 equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), 0.2 mLdimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 65° C.for 18 h. Concentration of the reaction mixture and purification of theresulting residue via Kugelrohr distillation (120 mTorr, 65° C.) gave65.4 mg (63% yield) of 4o as a colorless oil. Note: product is volatileunder high vacuum. (Note: the purified material obtained by Kugelrohrdistillation was accompanied by ca. 5% unidentified by-products;however, further purification by chromatography was precluded by theinstability of 4o on SiO₂). ¹H NMR (500 MHz, Benzene-d6) δ 7.63-7.58 (m,2H), 7.27-7.19 (m, 3H), 3.40 (d, J=6.4 Hz, 2H), 0.95 (ttt, J=8.0, 6.4,4.9 Hz, 1H), 0.34 (s, 6H), 0.32-0.28 (m, 2H), 0.12-0.05 (m, 2H). ¹³C NMR(126 MHz, Benzene-d6) δ 138.63, 133.92, 129.80, 128.15, 67.54, 13.68,3.23, −1.38. IR (Neat Film NaCl) 3070, 3006, 2958, 2862, 1470, 1427,1403, 1251, 1177, 1116, 1073, 851, 826, 785, 740, 699 cm⁻¹; HRMS (EI+)calc'd for C₁₂H₁₈OSi [M+•]: 206.1127, found 206.1148.

Example 2.2.24. Dimethyl(oxiran-2-ylmethoxy)(phenyl)silane 4p

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), glycidol (37 mg, 0.5 mmol, 1.0 equiv),PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL oftetrahydrofuran (THF) at 25° C. for 18 h. The desired product 4p (74.8mg, 72% yield) was obtained as a colorless oil by silica gel flashchromatography (10% EtOAc in hexanes). R_(f)=0.60 (10% EtOAc inhexanes); ¹H NMR (500 MHz, Benzene-d₆) δ 7.63-7.53 (m, 2H), 7.22 (dd,J=5.5, 1.8 Hz, 3H), 3.58 (dd, J=11.9, 2.9 Hz, 1H), 3.33 (dd, J=11.9, 5.3Hz, 1H), 2.78 (ddt, J=5.4, 3.9, 2.7 Hz, 1H), 2.24 (dd, J=5.3, 4.0 Hz,1H), 2.16 (dd, J=5.3, 2.6 Hz, 1H), 0.33 (s, 6H). This compound has beenpreviously characterized. See Bideau, F. L., et al., ChemicalCommunications (Cambridge, United Kingdom), 2001, 15, 1408-1409

Example 2.2.25. (((3s,5s,7s)-Adamantan-1-yl)oxy)dimethyl(phenyl)silane4q

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 1-adamantol (76 mg, 0.5 mmol, 1.0 equiv),PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL oftetrahydrofuran (THF) at 65° C. for 18 h. The desired product 4q (66.2mg, 60% yield) was obtained as a colorless oil by removal of volatilesat 80° C. at 60 mTorr. ¹H NMR (500 MHz, CDCl₃) δ 7.68-7.62 (m, 2H),7.40-7.38 (m, 3H), 2.13-2.08 (m, 3H), 1.80 (dt, J=3.3, 0.8 Hz, 6H),1.64-1.55 (m, 6H), 0.43 (s, 6H). This compound has been previouslycharacterized. See Park, J.-W., et al., Organic Letters, 2007, vol. 9(20), 4073-4076.

Example 2.2.26. Dimethyl(phenoxy)(phenyl)silane 4r

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), phenol (47 mg, 0.5 mmol, 1.0 equiv),PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL ofdimethoxyethane (DME) at 65° C. for 24 h. The desired product 4r (101.6mg, 89% yield) was obtained as a colorless oil by silica gel flashchromatography (5% EtOAc in hexanes). R_(f)=0.42 (5% EtOAc in hexanes);¹H NMR (500 MHz, CDCl₃) δ 7.75-7.71 (m, 2H), 7.52-7.47 (m, 3H),7.31-7.24 (m, 2H), 7.05-7.00 (m, 1H), 6.93-6.88 (m, 2H), 0.61 (s, 6H).This compound has been previously characterized. See Homer, L., et al.,Journal of Organometallic Chemistry, 1985, 282, 155-174.

The same reaction was conducted using NaOH (10 mol %), PhMe₂SiH (1.5equiv) in THF at 45° C. for 48 hours to provide 4r in a yield of 85%

Example 2.2.27. (4-Methoxyphenoxy)dimethyl(phenyl)silane 4s

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), 4-methoxyphenol (62 mg, 0.5 mmol, 1.0equiv), PhMe₂SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), 0.2 mLdimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 65° C.for 18 h. The desired product 4s (106.0 mg, 82% yield) was obtained as acolorless oil by silica gel flash chromatography (5% EtOAc in hexanes).R_(f)=0.45 (5% EtOAc in hexanes); ¹H NMR (500 MHz, CDCl₃) δ 7.63 (dd,J=7.8, 1.7 Hz, 2H), 7.45-7.36 (m, 3H), 6.74 (s, 4H), 3.74 (s, 3H), 0.50(s, 6H); ¹³C NMR (126 MHz, CDCl₃) δ 154.32, 148.85, 137.40, 133.61,130.00, 128.06, 120.73, 114.57, 55.70, −1.11. IR (Neat Film NaCl) 3420,2958, 2833, 1638, 1505, 1465, 1441, 1427, 1253, 1233, 1118, 1037, 911,831, 787, 729, 700 cm⁻¹; HRMS (EI+) calc'd for C₁₅H₁₈O₂Si [M+•]:258.1076, found 258.1083.

Example 2.2.28. Di-tert-butyl(phenoxy)silane 7

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), phenol (47 mg, 0.5 mmol, 1.0 equiv),(t-Bu)₂SiH₂ (108 mg, 148 μL, 0.75 mmol, 1.5 equiv), 0.25 mLdimethylformamide (DMF) and 0.25 mL of tetrahydrofuran (THF) at 65° C.for 24 h. The desired product 7 (106.5 mg, 90% yield) was obtained as acolorless oil by silica gel flash chromatography (5% EtOAc in hexanes).R_(f)=0.77 (5% EtOAc in hexanes); ¹H NMR (500 MHz, CDCl₃) δ 7.26-7.21(m, 3H), 6.95-6.93 (m, 2H), 4.44 (s, 1H), 1.07 (s, 18H). This compoundhas been previously characterized. See Huang, C., et al., Journal of theAmerican Chemical Society, 2011, 133 (32), 12406-12409.

Example 2.2.28. 2,4,4,5,5-Pentamethyl-2-phenyl-1,3,2-dioxasilolane 13

The general procedure was followed. The reaction was performed with NaOH(40.0 mg, 1.0 mmol, 10 mol %), pinacol (1.18 g, 10.0 mmol, 1.0 equiv),MePhSiH₂ (1.83 g, 2.06 mL, 15.0 mmol, 1.5 equiv), and 10.0 mL oftetrahydrofuran (THF) at 25° C. for 20 h. Concentration of the reactionmixture and purification of the resulting residue via Kugelrohrdistillation (150 mTorr, 120° C.) gave 2.19 g (93% yield) of 13 as acolorless oil. Note: product is volatile under high vacuum. ¹H NMR (500MHz, Benzene-d6) δ 7.77-7.71 (m, 2H), 7.20-7.17 (m, 3H), 1.22 (s, 6H),1.16 (s, 6H), 0.43 (s, 3H); ¹³C NMR (126 MHz, CDCl₃) δ 136.58, 134.03,130.42, 128.21, 81.80, 26.03, −0.35. IR (Neat Film NaCl) 3441, 3071,2980, 1643, 1464, 1428, 1366, 1260, 1161, 1121, 1026, 793, 736, 699cm⁻¹; HRMS (EI+) calc'd for C₁₃H₂₀O₂Si [M+•]: 236.1233, found 236.1237.

Example 2.2.29.(3-((Dimethyl(phenyl)silyl)oxy)prop-1-yn-1-yl)dimethyl(phenyl)silane 4x

The general procedure was followed. The reaction was performed with NaOH(2.0 mg, 0.05 mmol, 10 mol %), prop-2-yn-1-ol (28 mg, 0.5 mmol, 1.0equiv), PhMe₂SiH (204 mg, 230 μL, 1.5 mmol, 3.0 equiv), and 0.5 mL of1,2-dimethoxyethane (DME) at 45° C. for 24 h. The desired product 4x(142.9 mg, 88% yield) was obtained as a colorless oil after solventremoval at 85° C. at 45 mtorr for 30 minutes. Careful heating isnecessary, as the product is volatile under these conditions. ¹H NMR(500 MHz, CDCl₃) δ 7.62 (ddt, J=6.4, 1.8, 0.9 Hz, 4H), 7.44-7.36 (m,6H), 4.35 (s, 2H), 0.48 (s, 6H), 0.43 (s, 6H); ¹³C NMR (126 MHz, CDCl₃)δ 137.08, 136.80, 133.82, 133.73, 129.93, 129.57, 128.01, 127.98,105.77, 88.23, 52.27, −0.93, −1.36. IR (Neat Film NaCl) 3069, 3049,2959, 2177, 1428, 1363, 1250, 1117, 1085, 1043, 1004, 817, 782, 731, 698cm⁻¹; HRMS (EI+) calc'd for C₁₉H₂₃OSi₂ [(M+H)−H₂]: 323.1288, found323.1297.

Example 2.2.30.(((8R,9S,13S,14S,17S)-17-((dimethyl(phenyl)silyl)ethynyl)-3-methoxy-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-yl)oxy)dimethyl(phenyl)silane 10a

The general procedure was followed. The reaction was performed with KOH(2.8 mg, 0.05 mmol, 10 mol %), mestranol((8R,9S,13S,14S,17R)-17-ethynyl-3-methoxy-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenan-thren-17-ol)(155 mg, 0.5 mmol, 1.0 equiv), PhMe₂SiH (204 mg, 230 μL, 1.5 mmol, 3.0equiv), and 0.5 mL of 1,2-dimethoxyethane (DME) at 45° C. for 24 h then65° C. for 48 h. The product 10a (185.5 mg, 64% yield) was obtained as acolorless oil by silica gel flash chromatography (1%→5% EtOAc inhexanes). R_(f)=0.50 (5% EtOAc in hexanes); ¹H NMR (500 MHz, THF-d8) δ7.62-7.56 (m, 4H), 7.30 (dtq, J=9.6, 5.1, 2.2 Hz, 6H), 7.16 (d, J=8.6Hz, 1H), 6.63 (dd, J=8.5, 2.7 Hz, 1H), 6.59-6.55 (m, 1H), 3.69 (d, J=1.0Hz, 3H), 2.88-2.75 (m, 2H), 2.42-2.23 (m, 2H), 2.18 (qd, J=10.8, 10.1,3.5 Hz, 1H), 2.11-1.95 (m, 2H), 1.94-1.85 (m, 1H), 1.83-1.74 (m, 2H),1.54-1.38 (m, 4H), 1.34 (ddt, J=24.2, 12.3, 5.9 Hz, 1H), 0.94 (d, J=2.0Hz, 3H), 0.52-0.43 (m, 6H), 0.38-0.32 (m, 6H). ¹³C NMR (126 MHz, THF-d8)δ 158.87, 140.78, 138.42, 134.65, 134.38, 133.09, 130.31, 129.98,128.73, 128.45, 127.12, 114.47, 112.88, 112.37, 90.44, 82.68, 55.34,51.46, 49.86, 45.16, 41.66, 40.95, 34.17, 30.86, 28.64, 27.69, 24.01,17.10, 13.81, 1.44, −0.61. IR (Neat Film NaCl) 3417, 3068, 3048, 2946,2869, 2234, 2160, 2081, 1610, 1575, 1500, 1465, 1427, 1279, 1252, 1136,1117, 1088, 1045, 929, 886, 818, 783, 730, 699, 642 cm⁻¹; HRMS (EI+)calc'd for C₃₇H₄₇O₂Si₂ [M+H]: 579.3115, found 579.3109.

Example 2.2.31. Procedure for the Silylation ofWater—2,2,4,4,6,6-Hexaethyl-1,3,5,2,4,6-trioxatrisilinane 2j

To a solution of diethylsilane (0.5 mL, 3.85 mmol, 1.0 equiv) in THF(2.0 mL) was added NaOH (15.4 mg, 0.39 mmol, 10 mol %) and H₂O (1.0 mL,55 mmol, 15 equiv). The vial was then sealed and the mixture was stirredat 25 C for 24 h. The reaction mixture was diluted with 2 mL Et₂O andanalyzed by GC-MS, in which2,2,4,4,6,6-hexaethyl-1,3,5,2,4,6-trioxatrisilinane was the majorproduct observed (mass=306.2). Several other larger ring sizes wereobserved in smaller amounts.

Example 2.2.32. Procedure for Cross-Coupling Using2,4,4,5,5-Pentamethyl-2-phenyl-1,3,2-dioxasilolane 13 to Form1-phenyl-1H-benzo[d]imidazole 15

To a mixture of the PhSi^(Me)(pin) reagent 13 (freshly prepared, 71.0mg, 0.3 mmol, 2.0 equiv), benzimidazole 14 (17.6 mg, 0.15 mmol, 1.0equiv) and Cu(OAc)₂ (30.0 mg, 0.165 mmol, 1.1 equiv) in DMF (1.5 mL) wasadded TBAF (0.3 mL, 1.0M solution in THF) dropwise at 25° C. The mixturewas allowed to stir for 36 h at 250 C, after which NaHCO₃ saturatedsolution (2.0 mL) is carefully added and then the mixture waspartitioned between EtOAc and hexanes (5.0 mL each). The aqueous layerwas extracted with a 1:1 EtOAc:hexanes mixture (2×15 mL) then thecombined organic layers were washed with H₂O (2×10 mL) and brine (1×10mL), then dried over MgSO₄. The mixture was then filtered, the solventwas removed, and the resulting residue was purified via silica gel flashchromatography (gradient 20% EtOAc in hexanes to 70% EtOAC in hexanes)to yield a colorless solid (21.2 mg, 71% yield). R_(f)=0.25 (20% EtOAcin hexanes); ¹H NMR (500 MHz, CDCl₃) δ 8.16 (s, 1H), 7.93-7.84 (m, 1H),7.65-7.42 (m, 6H), 7.39-7.31 (m, 2H). This compound has been previouslycharacterized. See Cheng, C., et al., Science, 2014, 343, 853-857.

Example 3. Discussion Example 3.1. Using Benzyl Alcohol

Simple benzyl alcohol was chosen as the model substrate for initialstudies along with PhMe₂SiH as an inexpensive and abundantly availablesilicon source (Table 1). The reaction proceeded in THF as the solventwith 10 mol % NaOH as the catalyst to afford 94% yield of the desiredbenzyl silyl ether 2a at ambient temperature. The reaction could beperformed without regard for air and moisture with an identical yield;however some siloxane ((PhMe₂Si)₂O), arising from hydrolytic oxidationand subsequent coupling of the hydrosilane in the presence ofadventitious H₂O, was produced as a byproduct.

TABLE 1 NaOH-catalyzed dehydrogenative Si—H/O—H cross coupling: scope ofthe hydrosilane^(a,e)

2a 25° C. 94% yield

2b 45° C. 91% yield

2c 25° C. 82% yield

2d 65° C. 60% yield^(b,c)

2e 25° C. 96% yield

2f 65° C. 85% yield^(b)

2g 25° C. 67% yield^(d)

2h 25° C. 80% yield

2i 25° C. 95% yield

2j 25° C. (major product by GC-MS) ^(a)Reactions performed with 0.5 mmolof starting material and 0.5 mL of THF at the prescribed temperature.^(b)A 1:1 mixture of DMF/THF was used as the solvent. ^(c)3.0 equiv. ofhydrosilane and 20 mol % NaOH. ^(d)The reaction is conducted for 24 h.^(e)Yield of isolated material after purification.

Investigations of a wider scope of the hydrosilane showed that a numberof sterically and electronically diverse hydrosilanes were amenable tothe disclosed cross-coupling reaction (Table 1, 2a-2g). It was foundthat the use of DMF as a co-solvent was sometimes necessary to obtainhigh yields. It is noted here that DMF can also a role in transitionmetal-catalyzed dehydrogenative Si—O couplings. See Crusciel, J. J. Can.J. Chem. 2005, 83, 508-516. The use of di-tert-butyl silane led toefficient mono-silylation generating 2e in high yield; however, the useof less sterically hindered dihydrosilanes led to Si-tethered species 2hand 2i at ambient temperature. Remarkably, the cross-dehydrogenativeO—Si coupling tolerated sensitive disilanes such as H—Si₂(CH₃)₅ leadingto product 2g. In certain embodiments, then, the disclosed methods arealso useful for appending polysilanes onto small molecules andhydroxy-containing surfaces of for example polymers (e.g., polyvinylalcohol) and/or hydrated inorganic oxides (e.g., hydrated silica,alumina, etc., including surfaces comprising these hydrated oxides),which is especially valuable given the importance of Si—Si oligomers andpolymers in materials science applications, as described in Fujiki, M.Polymer Journal 2003, 35, 297-344. Additionally, the reaction ofdiethylsilane with water under NaOH catalysis resulted in the formationof cyclic siloxanes, with the trisiloxane 2j being the major product byGC-MS analysis. These products are precursors to valuable polysiloxanes,as described for example in Hunter, M. J., et al., J. Am. Chem. Soc.,1946, 68, 667-672

Example 2.2. Extending Alcohol Scope

Table 2 provides a sampling of the wide variety of hydroxyl-containingsmall molecules useful in the present methods. The disclosedcross-dehydrogenative coupling was amenable to substrates containingaromatic (Table 2, entries 1-11, 19, and 20) as well as aliphatic(entries 12, 15, and 17-20) moieties. The reaction proceeded well in thepresence of arenes bearing halides (Table 1, entries 2 and 3), nitro-(entry 4), ether (entry 6), and alkyl (entry 10) functionalities leadingto the corresponding silyl ethers in generally high yields. Moleculescontaining electron poor- (entry 7) and electron rich aromaticheterocycles (entries 8 and 9) were likewise excellent substrates forthe dehydrocoupling. A secondary allylic alcohol (entry 13) and aninternal alkyne (entry 15) also reacted well, with no reduction orhydrosilylation of the C—C multiple bonds detected. Strained rings(entries 16, and 17) were likewise tolerated with no undesired ringopening observed. Even the tertiary alcohol 1-adamantol (entry 18) wasresponsive to the dehydrocoupling yielding the silyl ether in excellentyield. The disclosed silylation methods were also amenable to thesilylation of phenols, generating the corresponding silylated productsin good yields (entries 19 and 20), though under somewhat more demandingreaction conditions.

Moreover, the functionalities such as an aromatic methyl ester (entry 5)and a phthalimide (entry 11), which are known to readily undergohydrosilylation or direct reduction in the presence of Lewis bases andhydrosilanes, remain intact under these reaction conditions giving 4eand 4k respectively with no undesired hydrosilylation or reductiondetected. This further demonstrated that the disclosed O—Sicross-dehydrocoupling is complementary to alternative methods in termsof scope and practicality and is evidence of the method's mildconditions and broad tolerance of sensitive functionalities.

TABLE 2 Scope of the alcohol partner^(a,d,e)

Entry Silylated Product T (° C.) Yield  1 R = H 25 2a (94%)  2  3  4  5 6

R = 4-F R = 4-Br R = 4-NO₂ R = 4-CO₂Me R = 4-OMe 25 65 65 65 25 4a (79%)4b (91%) 4c (71%) 4d (84%)^(b) 4e (87%)  7

25 4f (97%)  8

25 4g (96%)  9

45 4h (87%) 10

65 4i (92%)^(b) 11

65 4j (62%) 12

25 4k (64%) 13

45 4l (92%)^(b) 14

45 4m (98%) 15

45 4n (86%) 16

65 4o (70%) 17

25 4p (72%) 18

65 4q (96%) 19

65 4r (89%)^(c) 20

65 4s (82%) ^(a)Reactions performed with 0.5 mmol of starting materialand 0.5 mL of THF at the prescribed temperature. ^(b)2:3 DMF/THF used asthe solvent. ^(c)3.0 equiv. hydrosilane, 20 mol % NaOH, DME [1.0 M]solvent. ^(d)[Si] = PhMe₂SiH. ^(e)Yield of isolated material afterpurification. ^(f)Base-catalyzed transesterification by the pendantalcohol occurred with this substrate, resulting in a separable mixturecontaining approximately a 1:5 ratio of silylated dimer:silylatedmonomer; the combined silylated yield was 84%.

Example 3. Introduction of Silyl Ethers as Directing Groups

The disclosed cross-dehydrogenative silylation also proved to be aconvenient one-step installation of directing groups of value in organicsynthesis (Table 3).

TABLE 3 Applications to directing group chemistry ^(a,b)

^(a) Reaction performed with 0.5 mmol of starting material and 0.5 mL ofTHF. ^(b) Yield of isolated material after purification. Ref 6a refersto the methods described in Huang, C., et al., J. Am. Chem. Soc. 2011,133, 12406-12409; Ref 6b refers to the methods described in Huang, C.,et al., J. Am. Chem. Soc. 2011, 133, 17630-17633, both of which areincorporated by reference for their teachings of these methods.

For example, the reaction of phenol 5 with the bulky and commerciallyavailable di-tert-butylsilane 6 with 10 mol % NaOH furnished thecorresponding di-tert-buylhydrosilyl ether 7 in high yield and withoutundesirable double activation of the Si—H bond, which would haveotherwise led to the formation of 7a (Table 3). Silane 7 was readilyadvanced to silanol 8, which contains a directing group forpalladium-catalyzed C—H functionalization reactions such asortho-oxidation to generate catechols (Table 3, 8→9) andortho-alkenylation to access α-hydroxy styrenes (8→10).

Cognizant of the importance of heteroatom-substituted arylsilanes in C—Cand C—X bond-forming reactions, the catalytic Si—O bond constructionmethod was tested for the expedient and cost-efficient synthesis ofnovel cross-coupling reagents. Toward this aim, the silicon analogue ofPhB(pin)-Ph^(Me)Si(pin) (Table 4, 13) where Me is chosen as anon-transferrable group—was prepared and evaluated for its suitabilityas an aryl transfer reagent. This would be beneficial given theincreased abundance and lower cost of Si relative to B, and thepotential for improved stability or overall utility of the siliconreagent. However, these efforts faced the potential challenges of aone-step preparation of the proposed silicon-based aryl transfer reagentinvolving a silylene protection of a 1,2-diol, which is challenging,even in the case of simple, non-sterically hindered diols. Poorcyclization reactivity, uncontrollable oligomerization, orrearrangements, all of which are known to occur. Prior to the presentefforts, this compound has only been prepared by two strategies:refluxing pinacol in THF for 24 h with a) the dichlorosilane in thepresence of stoichiometric pyridine, or b) the dihydrosilane in thepresence of a catalytic quantity of Cp₂TiCl₂/n-BuLi. The yields were20-50% and 67% respectively and the product was not fully characterized.The success of the efforts described herein, based on the mild catalystsystem disclosed herein provide a convenient route toward theseinteresting dioxasilacycles and their derivatives.

Thus, combining the commercially available and inexpensive SiPhMeSiH₂ 11with the di-tertiary 1,2-diol pinacol 12 in a 1:1 stoichiometry atambient temperature resulted in the immediate and vigorous evolution ofhydrogen upon addition of NaOH (10 mol %).

TABLE 4 Multi-gram scale catalytic synthesis of PhSiMe(pin) anddiscovery of an aryl transfer reagent ^(a,b,c)

^(a) Reactions performed with 0.5 mmol of starting material and 0.5 mLof THF at the prescribed temperature. ^(b) Cu-mediated reactionperformed on 0.5 mmol scale. ^(c) Yield of isolated material afterpurification.

Surprisingly, the reaction was complete in 20 hours, giving a high yield(2.19 grams, 93% yield) of the corresponding colourless, distillable oilPhSi^(Me)(pin) 13 (Scheme 3, 11→13). No oligomers, polymers, oruncyclized products were detected. With this compound in hand, itsability to transfer the phenyl moiety bound to silicon in a Hiyama-typecross-coupling reaction could finally be investigated. To test this, thePhSi^(Me)(pin) reagent was treated with benzimidazole 14, Cu(OAc)₂, andTBAF and the mixture was stirred at ambient temperature for 36 h toprovide the desired N-arylation product 15 in 71% yield. Comparing theseresults with the 74% yield reported in C. Cheng and J. F. Hartwig,Science, 343 (6173), 853-857 (2014) using1,2-dimethyl-4-(1-methyl-2-trimethylsilanyl-1-trimethylsilanyloxy-ethyl)-benzeneunder comparable conditions demonstrates the ability of these pinacol(and related) derivatives to react in a similar fashion with Cheng'sR—SiMe(OTMS)₂ derivatives, including for example cross coupling witharyl halides to form biaromatics, addition of silylarenes to acrylates,and amination of benzimidizoles. The ability to provide a convenient andhigh-yielding catalytic silylene protection of pinacol is demonstrated,generating Ph^(Me)Si(pin) in a single step from commercially availablematerials, provides an intriguing complement to boron-basedcross-coupling reagents.

As those skilled in the art will appreciate, numerous modifications andvariations of the present invention are possible in light of theseteachings, and all such are contemplated hereby. All references citedwithin this disclosure are incorporated by reference herein for allpurposes, or at least for their teachings in the context presented.

What is claimed:
 1. A compound of formula:

wherein X is H or OH; p is 0 or 1; each R^(B) is independently atertiary alkyl; and (Het)Aryl is an optionally substituted phenyl,naphthyl, or 5- or 6-membered heteroaryl.
 2. The compound according toclaim 1, wherein X is H.
 3. The compound according to claim 1, wherein Xis OH.
 4. The compound according to claim 1, wherein p is
 0. 5. Thecompound according to claim 1, wherein p is
 1. 6. The compound accordingto claim 1, wherein at least one R^(B) is tert-butyl.
 7. The compoundaccording to claim 1, wherein the optional substituent is independentlyhalo, optionally protected hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₂-C₂₄alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy, C₆-C₂₄ aralkyloxy, C₆-C₂₄alkaryloxy, C₁-C₂₄ alkylcarbonyl (—CO-alkyl), C₆-C₂₄ arylcarbonyl(—CO-aryl)), C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl), C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl ((CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)-X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), optionally protected carboxy (—COOH), carboxylato(—COO—), optionally protected carbamoyl (—(CO)—NH₂), mono-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₁-C₂₄haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄ aryl)substitutedcarbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄aryl)-substituted carbamoyl, thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄alkyl)-substituted thiocarbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄alkyl)-substituted thiocarbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)substituted thiocarbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl, carbamido(—NH—(CO)—NH₂), cyano(-C≡N), cyanato (—O—C═N), thiocyanato (—S—C═N),formyl (—(CO)—H), thioformyl (—(CS)—H), optionally protected amino(—NH₂), optionally protected mono-(C₁-C₂₄ alkyl)-substituted amino,di-(C₁-C₂₄ alkyl)-substituted amino, optionally protected mono-(C₅-C₂₄aryl)substituted amino, di-(C₅-C₂₄ aryl)-substituted amino, C₁-C₂₄alkylamido (—NH—(CO)-alkyl), C₆-C₂₄ arylamido (—NH—(CO)-aryl), imino(—CR═NH where R=hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, orC₆-C₂₄ aralkyl), C₂-C₂₀ alkylimino (—CR═N(alkyl), where R=hydrogen,C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄ aralkyl), arylimino(—CR═N(aryl), where R=hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), nitro (—NO₂), nitroso (—NO), optionallyprotected sulfo (—SO₂OH), sulfonate(SO₂O—), C₁-C₂₄ alkylsulfanyl(—S-alkyl; also termed “alkylthio”), C₅-C₂₄ arylsulfanyl (—S-aryl; alsotermed “arylthio”), C₁-C₂₄ alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄arylsulfinyl (—(SO)-aryl), C₁-C₂₄ alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄monoalkylaminosulfonyl-SO₂—N(H) alkyl), C₁-C₂₄dialkylaminosulfonyl-SO₂—N(alkyl)₂, C₅-C₂₄ arylsulfonyl (—SO₂-aryl),boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂ where R is alkyl orother hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato (—P(O)(O)₂),phosphinato (P(O)(O—)), phospho (—PO₂), phosphine (—PH₂), optionallysubstituted C₁-C₂₄ alkyl, optionally substituted C₂-C₂₄ alkenyl, C₂-C₂₄alkynyl, and/or optionally substituted C₅-C₂₄ aryl.
 8. The compoundaccording to claim 1, wherein the optional substituent is independentlyan aldehyde (CHO), C₁₋₆ alkyl, C₁₋₆ alkylcarbonyl (—C(O)—C₁₋₆alkyl),C₁₋₆ alkoxy, C₁₋₆ alkoxycarbonyl (—C(O)—C₁₋₆alkyl), —C(O)—C₆₋₂₄ aryl),—C(O)-(5- or 6 membered heteroaryl), halo, nitrile, nitro, a fused 5- or6 membered carbocyclic ring and/or a fused 5- or 6 membered mono- ordiether ring.
 9. The compound according to claim 1, wherein (Het)Aryl isan optionally substituted phenyl.
 10. The compound according to claim 9,wherein said compound is a compound of the formula:

wherein X is H or OH; n is 0, 1, 2, 3, 4, or 5, and R^(A) is aldehyde(—CHO), C₁₋₆ alkyl, C₁₋₆ alkylcarbonyl (—C(O)—C₁₋₆alkyl), C₁₋₆ alkoxy,C₁₋₆ alkoxycarbonyl (—C(O)—C₁₋₆alkyl), —C(O)—C₆₋₂₄ aryl), —C(O)-(5- or 6membered heteroaryl), halo, nitrile, or nitro; or wherein two R^(A)'stogether with the phenyl ring form a fused 5- or 6 membered carbocyclicring or 5- or 6 membered mono- or diether ring.
 11. The compoundaccording to claim 10, wherein X is H.
 12. The compound according toclaim 10, wherein X is OH.
 13. The compound according to claim 1,wherein (Het)Aryl is an optionally substituted naphthyl.
 14. Thecompound according to claim 1, wherein (Het)Aryl is an optionallysubstituted 5- or 6-membered heteroaryl.
 15. The compound according toclaim 14, wherein X is H.
 16. The compound according to claim 14,wherein X is OH.
 17. The compound according to claim 14, wherein p is 0.18. The compound according to claim 14, wherein p is
 1. 19. The compoundaccording to claim 14, wherein at least one R^(B) is tert-butyl.
 20. Thecompound according to claim 1, wherein (Het)Aryl is an optionallysubstituted a furan, pyrrole, thiophene, pyrazole, imidazole, triazole,isoxazole, oxazole, thiazole, isothiazole, oxadiazole, pyridine,pyridazine, pyrimidine, pyrazine, triazone, benzofuran, benzopyrrole,benzothiophene, isobenzofuran, isobenzopyrrole, isobenzothiophene,indole, isoindole, indolizine, indazole, azaindole, benzisoxazole,benzoxazole, quinoline, isoquinoline, cinnoline, quinazoline,naphthyridine, 2,3-dihydrobenzofuran, 2,3-dihydrobenzopyrrole,2,3-dihydrobenzothiophene, dibenzofuran, xanthene, dibenzopyrol, ordibenzothiophene.